Accepted Manuscript

Title: Current Status, Opportunities and Challenges in

Catalytic and Photocatalytic Applications of Aerogels:
Environmental Protection Aspects

Author: Hajar Maleki Nicola Hüsing

PII: S0926-3373(17)30748-8
DOI: http://dx.doi.org/doi:10.1016/j.apcatb.2017.08.012
Reference: APCATB 15930

To appear in: Applied Catalysis B: Environmental

Received date: 15-5-2017

Revised date: 22-7-2017
Accepted date: 2-8-2017

Please cite this article as: H. Maleki, N. Hddotusing, Current Status, Opportunities
and Challenges in Catalytic and Photocatalytic Applications of Aerogels:
Environmental Protection Aspects, Applied Catalysis B, Environmental (2017),
http://dx.doi.org/10.1016/j.apcatb.2017.08.012

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Current Status, Opportunities and Challenges in Catalytic and Photocatalytic Applications

of Aerogels: Environmental Protection Aspects

Hajar Maleki, Nicola Hüsing

b
Institute of Materials Chemistry, Paris-Lodron University Salzburg, Jakob-Haringer-Strasse 2a, 5020,

t
Salzburg, Austria

ip
Corresponding authors:
HM: hajar.maleki@sbg.ac.at

cr
NH: Nicola.Huesing@sbg.ac.at

Abstract

us
Aerogels are the exceptional class of materials which have been drawing attentions for several
high-performance applications thanks to their extraordinary physical properties such as
an
extremely high porosity, high specific surface area, and extremely low density as well as their
versatile synthesis approach along with their tunable bulk properties. Since their invention by
M
Kistler, various aerogels have been explored for the catalytic and photocatalytic applications,
though in the recent decades, a breakthrough from different aspects ranging from efficient
catalysis of organic synthesis, energy-related process, and catalytic environmental depollution by
d

aerogels have been made. For both catalytic and photocatalytic performances, aerogel monoliths
e

prepared from sol-gel approach accompanied with an appropriate drying technique, in particular,
supercritical point drying have become striking alternative catalysts or catalyst supports
pt

compared to the present catalyst supports prepared from traditional wet synthesis approaches. In
ce

this article, the aerogel contributions in the environmental remediation processes as

heterogeneous catalyst and photocatalyst for depollution of air and aqueous media are fully
addressed, and recent achievement in this context are thoroughly reviewed.
Ac

Keywords: aerogel catalyst, aerogel photocatalyst, environmental remediation, air cleaning,

water cleaning

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Page 1 of 96
 Content
1. Introduction

2. Synthesis

2.1. Principle of sol-gel process

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2.2. Synthesis of aerogels

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3. Catalytic applications of aerogel for air cleaning

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3.1 DeNOx application

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3.2 VOCs combustion

3.3 Methane reforming with CO2

3.4 Preferential oxidation (PROX) of CO

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3.5 Aerogel photocatalysts in air cleaning
M
4. Catalytic applications of aerogels for removal of aqueous pollutants

4.1. Advanced Oxidation Processes (AOPs)

d

4.1.1 Fenton and Fenton-like process

e
pt

4.1.2 Ozonation process

4.2. Photocatalysts in water cleaning

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5. Conclusions and outlooks

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1. Introduction

Aerogels are sol-gel derived porous materials with extraordinary properties, such as a high

porosity, extremely low density, enormous active surface area and very low thermal conductivity

[1]. The unique properties in aerogels have originated from the combination of the specific

properties of nanomaterials magnified by their macroscale self-assembly making aerogels

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Page 2 of 96
attractive materials for several potential applications ranging from thermal and acoustic

insulation and catalysis to biomedical and pharmaceutical applications [2-4]. Amongst high-

performance applications, e.g. as thermal insulators [4, 5], aerogels have been recognized as

catalysts or catalyst supports in various reactions [6, 7].

t
ip
Historically, the first aerogels were introduced by Kistler in the 1930’s [8] by applying the

supercritical drying method for the first time. However, in the following years, due to the

cr
progress in precursor chemistry and drying methods, various aerogels having organic as well as

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inorganic or even hybrid building blocks emerged [9]. Basically, irrespective of the building

blocks and components, aerogel refers to solid materials having a three-dimensional porous
an
network with interconnected micro/ mesopores obtained by drying technologies that are able to

conserve the initial wet gel structure [1].

M
Following the major interest of chemical industry in designing innovative materials as a solid
d

catalyst, in recent years, a major interest has been given to tailor-made aerogels as heterogeneous
e

catalysts or catalyst supports for various reactions. In fact, Kistler [10] was a pioneer to
pt

recognize catalytic applications of aerogels which were later pursued by several scientists mainly

Teichner, Baiker, Pajonk, and other groups [11-16]. In the 90’s a series of reviews addressing the
ce

different gas and liquid phase catalytic aspects of aerogels particularly with the prospect of
Ac

environmental protections were published by the same scientists [6, 7]. So far, aerogels and their

composites have been employed in both liquid-solid, and gas-solid catalyzed reactions in several

domains, such as environmental protection, organic synthesis including partial oxidation,

epoxidation, nitroxidation, hydrogenation [16, 17] as well as energy-related applications [14, 15,

18-20]. Aerogels were also considered as solid biocatalysts for specific biochemical synthesis or

as an active component of biosensors [21-24].

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Page 3 of 96
Since the support is playing a pivotal role in catalysts design, the use of materials with

deliberately tailored properties is highly desirable. The suitability of aerogels as a catalyst

support is related to their fascinating textural and structural properties in combination with the

versatility of the synthesis route, e.g. the sol-gel technique, which gives a flexibility of

t
controlling the texture, composition, homogeneity and structural features of solids from a

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molecular level [12, 16, 20]. Additionally, the sol-gel technique opens up new possibilities to

cr
tailor the materials properties through the addition of different components, i.e. dispersion of the

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various oxides or metals in an aerogel matrix, to design and tailor the chemistry of aerogel

towards the particular catalytic reactions [20].

an
Catalysts are essential components for the treatment of air and water pollutants on the way to a

sustainable and clean environment [25]. Aerogels from various molecular precursors are
M
recognized as active heterogeneous catalysts for several catalytic and photocatalytic

environmental remediation purposes [6, 26, 27].

d

To preserve the air quality, control of the emission of hazardous volatile organic compounds
e

(VOCs), nitrogen oxides (NOx; NO, NO2, N2O, etc.), carbon monoxide (CO), greenhouse gases
pt

i.e. methane (CH4) and carbon dioxide (CO2), etc. being released from transportation, municipal
ce

and industrial sectors and combustion is necessary.

Nitrogen oxides, NOx gases are generated from the reaction of nitrogen, oxygen, and
Ac

hydrocarbons at high temperatures. The primary sources of NOx emission are traffic, industry,

refineries and power plants [28, 29]. Catalytic conversion of NOx into the less harmful gases,

such as N2 and H2O, is quite a matured field, and several review papers exist covering this topic

[30-32]. The selective catalytic reduction (SCR) of NOx with various reductants such as NH3,

hydrocarbons, CO and soot particles over various catalysts and catalyst supports are reported for

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Page 4 of 96
NOx abatement, so far [33]. However, ammonia or aqueous solutions of ammonia have been the

main reductants used in the selective reduction of NOx, especially in the gas turbines, power

plants, and waste incinerators [33]. In this contribution, we specifically focus on the SCR of NOx

using NH3 as a reductant by exploiting the vanadium supported various metal oxides or carbon

t
aerogel catalysts.

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Aerogels are also recognized as the suitable candidates for the adsorption/ absorption as well as

cr
catalytic combustion of VOC vapours from effluents due to their tunable textural e.g. high

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specific surface area and porosity and structural properties e.g. density and monolithic structures

as well as tunable surface chemistry [34]. In this paper, combustion catalysis of various VOCs
an
using the noble metal catalysts such as Pt, Pd, etc. supported carbon aerogels and transition metal

oxides is studied [26].

M
Aerogels are also attractive for CO removal from an enriched hydrogen stream which is

produced on board vehicles through different reforming and fuel oxidation processes [127] -
d

being hydrogen as an ideal fuel for proton-exchange membrane fuel cells (PEMFC). The
e

PEMFC has drawn significant attention due to the low operation temperature, high efficiency,
pt

high power density and its environmentally benign exhaust gases [126]. However, during
ce

hydrogen production, a significant amount of CO is produced that causes a serious poisoning of

the anode catalyst (e.g. platinum or palladium) of PEMFC. Therefore, it is necessary to remove
Ac

CO from hydrogen stream with a minimum loss of hydrogen [128]. So far, several strategies for

CO removal have been proposed [122], among them preferential oxidation of CO (CO-PROX) is

the most effective one which is a catalytic process [129, 130]. In this regard, inorganic aerogel

based on the noble metals as well as various bimetallic compounds supported inorganic aerogels

have shown better promises for CO-PROX compared to the conventional catalysts.

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Page 5 of 96
Aerogel contribution for methane reforming with CO2 is also discussed from the perspective of

environmental protection aspects, even though this process is more known for the production of

clean H2 energy and synthesis gases (CO/H2) as a feedstock for Fischer-Tropsch synthesis of

hydrocarbons. Noble metals, transition metals, and their bi-metallic doped metal oxide aerogels

t
have been exploited to catalyze the methane reforming process. Besides, catalyst preparation

ip
methods, structural parameters, coke resistivity and operational conditions like the type of the

cr
reactor are extremely influential in the efficiency of the process that would be elaborated in this

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review paper.

Photocatalyst technology using semiconductors mainly TiO2 or TiO2 based composites is another
an
effective way to deal with the problems concerning the pollutions abatement in gaseous

environments [35]. The ease of implementation in commercial settings as well as low energy
M
requirement that uses the sun or artificial light as the energy sources and applicability to wide

range of indoor and outdoor pollutants (i.e. NOx, VOC, bacteria, airborne particles and etc.)
d

make this process an attractive choice in the degradation of contaminants [36, 37]. However,
e

traditional methods of sample preparation for photocatalytic reactions using powder form
pt

samples are not efficient enough from catalyst regeneration, and consequently, from an economic
ce

and recycling standpoint [38]. Therefore, studies have shown that the preparation of

photocatalyst in a certain geometry with the high active surface area for instance in two - (e.g.
Ac

films) or three-dimensional structures (e.g. aerogels) for loading of the large amount of

photoactive phases without any loss in catalyst during the process is becoming a compelling and

critical issue [38, 39]. The photoactive aerogels like TiO2 and TiO2 supported silica or other

oxides aerogels are being actively explored for air pollutant capturing and photodecomposition

that is studied in details in this paper.

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Page 6 of 96
Another major threat to the environment and human health rely on water pollution. As

wastewaters contain a wide variety of pollutants including dyes or another complex organic

pollutant, eutrophication agents (e.g., nitrates, phosphates), metal cations, etc. Major sources of

water pollutants are those that are originated from the textile and dye manufacturing, chemical

t
and pharmaceutical industries, food technologies, oil refineries, petrochemical plants, and others

ip
[40]. Most of these contaminants are complex organic molecules or dyes that are often severely

cr
degraded or separated from the water sources. Several possible technologies based on physical,

us
biological and chemical methods have been exploited to eliminate these organic water

contaminants [2]. The utility of aerogels namely hydrophobic silica, carbon, cellulose, and
an
biomass derived aerogels for water treatment have been promising not only from the aspect of

physical and chemical adsorption but also with regards to the chemical degradation of the
M
hazardous compounds through a series of the catalytic advanced oxidation process namely

Fenton, Fenton like reactions as well as ozonation process. In these processes, the highly reactive
d

species like hydroxyl radicals are obtained which are responsible for the degradation of aqueous
e

pollutants, which would be elaborated from the aspect of utilizations of different aerogel
pt

catalysts.
ce

For an efficient catalytic degradation of aqueous pollutants on aerogel networks, initial

adsorption of contaminants from wastewaters would be extremely helpful. The high pollutant
Ac

adsorption efficiency can often be achieved by tailoring the physicochemical and textural

properties of the aerogel network, such as porosity, specific surface area, and surface

hydrophobicity. In this respect, a recent review article by us has extensively studied the

contaminants adsorption aspect of aerogels [2]. In the other hand, the mechanical strength caused

by the interwoven network in aerogel prevents the loss of active catalyst or active surface area.

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Page 7 of 96
Besides, the crack free aerogel monoliths can host photoactive phases that could provide an

efficient medium for photocatalytic oxidation of organic water pollutants.

This review gives an overview of all processes involved in the synthesis of different aerogel

catalysts and catalyst supports and, in a broader sense, a summary of their recent applications as

t
an environmental (photo)catalyst for removal of various pollutants from both air and water

ip
sources.  

cr
us
2. Synthesis

Basically, there are three steps involved in the preparation of aerogels including sol-gel
an
reactions, aging and drying processes. In the case of carbon aerogels, an additional carbonization

process is required [9].

M
d

2. 1. Principle of sol-gel process

e

The chemistry behind the formation of filigree aerogel network is followed by a sol-gel reaction.
pt

Generally speaking, a sol-gel reaction is a solution based synthesis method that is accompanied

by a transformation of the molecular precursor to the formation of colloidal solution (sol) to

ce

obtain a solid material (gel) by the addition of a chemical crosslinker or by changing the physical
Ac

conditions of the reaction e.g. pH, temperature. Figure 1 indicates the nearly global schematic

sol-gel reactions for the synthesis of materials in the forms of nanoparticulate powders as well as

self-supporting nanostructured monoliths having inorganic, organic and biobased molecular

structures.

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Page 8 of 96
The sol-gel process can be adapted to the both aqueous and non-aqueous based media [41].

Aqueous based sol-gel transition is basically the most predominant process and can be explained

by the hydrolysis (formation of hydroxyl groups) and condensation reactions (formation of e.g.

oxo bridges) of molecular precursors, e.g. metal alkoxides or inorganic salts, but also organic and

t
hybrid inorganic-organic monomers (M: metal, OR: alkoxy group) [42]. Silica-based sol-gel

ip
derived materials is a key example in this regards. Fig. 1 illustrates the sol-gel reaction of

cr
tetramethyl orthosilicate (TMOS) as a representative organosilane and its polymerization or

us
polycondensation contributing in the formation of the 3D network buildup.

an
M
e d
pt
ce
Ac

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Page 9 of 96
 Sol-gel processes:
Aqueous sol-gel process: O
OH
H H O
d d O Si Si
M(OR)z-1 HO O
O M(OR)z O Si O O O
O Si ''SiO 2 ''
H H O Si
O O OH
R Si O
O O Si O
Leaving group - H2 O , -CH3 OH
O Si
MOH(OR)z-1 ROH O O
Example: O
O Si O

t
O
O Si
Precursors: O

ip
O
Inorganic metal salts e.g. chloride, nitrate, sulfate, etc., - H2 O
and metal organic compound such as an alkoxide HO
O
Tetramethoxysilane (TMOS) Si
Products: O
O O

cr
Gels and Powders: SiO2 , TiO2 , ZrO 2, Al2 O3, V2O5, mixed O
O Si
oxides, etc. H2 O/ acidic or
O
basic catalysis
Inorganic or Nonaqueous sol-gel process:
inorganic-

us
a)
organic -RX + XnM X
YCh R XnM Ch R XnM Ch MXn MChx
based system
-RX Ch: chalcoginde (O,S)
XnM X
X: halogene
OH Cl Y: H or alkyl
Example: TiCl4 + 2 TiO2 + 2 + 2 HCl

b)
(RO)nM O R'

(RO)n M O R
-R'OR
(RO)nM O M(OR)n MOx
an
Example: Hf(OR)4 HfO2 + 2 R O R R: C6 H5 CH2 , CH2 CH3
M
Precursors:
Inorganic metals, metal alkoxides, metal acetates and metal
acetylacetonates
Products:
Gels and Powders: metal oxides and metal sulfides, binary metal oxides, etc.
d

Polymeric and carbonaceous system OH

Formaldehyde O Resorcinol-formaldehyde(RF)
OH polymer chains
e

OH OH O
O OH
Catalyst OH
+ 2 HO
HO
CH2 OH
pt

OH
HO OH Drying Carbonaceous
Resorcinol material
Carbonization/ Ar
OH OH
OH T> 600oC
Precursors: O
ce

Examples: OH OH

OH OH
organic,
biobased and N
carbonaceous HO OH
Acrylnitril
Ac

materials Phenol Phloroglucinol Phenol

Biopolymer system OH
O O
HO
-
Physical: pH or temperture OOC
OH
OH -OOC O
Molecular precursor: O
aqueous solution Gel (hydrogel)
O Ca2+
HO
(Sol) Example: O
Chemical: crosslinker like cations OH
COO-
Aginate chain Ca2+ HO
HO
O O COO-
Precursors: OH
Polysccharide: cellulose, chitosan, pectin, COO- sol-gel O
O O O
HO
alginate,.. HO O
O
Peptide: gelatin, soy, silk fibroin,.. COO- HO O
 

Fig.1 Schematic description of the sol-gel process.

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Page 10 of 96
This figure also illustrates some typical non-hydrolytic condensation reactions in which instead

of water, an organic oxygen donor e.g. alcohol, ether, carboxylic acid, etc. are used to build up

oxo bridges in the network. This process is a simple and quite well-adapted procedure for the

water-free synthesis of oxides and mixed oxides materials and involves a nucleophilic attack at

t
carbon centers, e.g. condensation reactions accompanied by alkyl halide, ester or ether

ip
elimination [43]. This approach can also be extended to the synthesis of metal sulfides

cr
(chalcogenides) by using thiol and thioether sulfur-donors. However, the explanation in this

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context is beyond the scope of this paper and can be conferred to the review of Mutin and Vioux

[43] who have highlighted the pros and cons of non-hydrolytic reaction over conventional sol-gel

reaction.   an
The sol-gel polycondensation to build up polymeric network e.g. resorcinol-formaldehyde
M
polymers proceed analogously in purely inorganic polymers in the presence of a basic catalyst

(cf. Fig. 1) [44]. Carbon or carbonaceous sol-gel based materials are also synthesized following
d

to the carbonization or pyrolysis process on dried polymeric monoliths/ materials. Figure 1 also
e

lists the typical representative monomers which are also used to prepare carbonaceous
pt

monolithic materials [42, 45]. For the biobased molecular precursors i.e. polysaccharides and
ce

polypeptides, the condensation proceeds in different ways through establishing physical

interactions like hydrogen bonds between polymer chains by e.g. changing in pH of media but
Ac

also with chemical crosslinking by the addition of a crosslinker to the reaction [46]. The alginate-

based polysaccharides condensation is an example in the regard of chemical crosslinking in

which gelation can take place by the crosslinking of the polymer chains with divalent cations

(i.e. Ca2+), following the so-called “egg-box” gelation model mechanism in which each cation is

coordinated by the carboxyl and hydroxyl groups of four guluronate building blocks from two

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Page 11 of 96
neighboring chains of the polymer (cf. Fig. 1) [46, 47]. The 3D network obtained in here is called

‘’aquagel’’ or ‘’hydrogel’’ that could be undergone later in the further process of the

transformation into highly porous gels or powders.

t
ip
2.2. Synthesis of aerogels – with an emphasis on aerogel catalysts

Unlike conventional approaches for preparing the multicomponent heterogeneous catalysts that

cr
require several cumbersome approaches of precipitation and impregnation, the sol-gel process

us
offers a couple of attractive features that are not achievable with classical wet chemistry

methods. A detailed overview of conventional synthesis approaches i.e. co-precipitation,

an
impregnation, and hydrothermal syntheses, etc. are provided in an all-embracing review by

Schwarz et al. [48]. Indeed, sol-gel process is a straightforward approach which allows
M
introducing several molecular precursors or even micro- or nanoparticles in the reaction mixture

at a single synthesis step. As a product of the sol-gel reaction, we will focus on the giving an
d

overview on aerogel monoliths preparation, and to this aim apart from the chemistry, we will
e
pt

also make an outline of different synthesis approaches of existed aerogel with an emphasis on

aerogel-based catalysts and catalyst supports giving a detailed discussion of each synthesis step.
ce

Until very recently, the most investigated materials forming fine aerogel structures are silica
Ac

(SiO2), polymer, carbon aerogels and various other types of aerogels together with their mixture.

If the functionality of aerogels was not enough for property demanded, additional components

like molecules, metal, oxide or polymer were impregnated to the aerogels preserving the porous

matrix.

Among the list of reported aerogels single oxide aerogels (e.g., Al, Ru, Ti, V, Cr, Fe, Sn, and Zr

oxide) [49-51], binary/ mixed oxides aerogels such as TiO2–SiO2 [52], ZrO2–SiO2 [53], Fe3O4-
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Page 12 of 96
SiO2 [54] and ternary composite aerogels such as V2O5–TiO2–SiO2, V2O5-Nb2O5-TiO2 [55] as

well as transition metal oxide doped aerogels containing Co, Cr, Mn, V, Fe, Cu, and Ni [56] have

been prepared for various heterogeneous catalytic reactions.

Different synthesis approaches leading to the preparation of aerogels, and their composites have

t
ip
been sufficiently studied in several review articles by Hüsing et al., Baiker et al., Maleki et al.

and Handbook of aerogels [1, 9, 16, 57]. However, Fig. 2 summarizes schematically possible

cr
routes that are proposed so far to prepare the mixed oxides, metal, and metal alloy doped metal

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oxides, oxide supported noble metals, as well as carbon and carbon, supported noble metal

aerogels which have been considered as heterogeneous catalysts and catalyst supports, so far.
an
According to the Figure 2i, during the sol-gel reactions, the first building blocks of the network
M
with sizes of ca. 1-10 nm are formed, which can now grow or aggregate in the further process.

This solution is referred as ‘’sol’’.

e d
pt
ce
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Page 13 of 96
 t
ip
cr
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an
M
e d

Fig. 2 Different procedures to prepare aerogel and aerogel composites based catalysts.
pt

The primary particles are involved in polycondensation and further network growth to give
ce

larger secondary nanoparticles or bigger aggregates that assemble to a three-dimensional

nanostructured gel network which is accompanied by the sol-to-gel transition in the reaction
Ac

mixture. The structural evolution and nanostructuration pattern of gel depends on the rate of

hydrolysis and condensation reactions as well as other reactions parameters such as pH value,

solvent type, water to alkoxide ratio, temperature and pressure [1].

Gelation does not imply that all precursors are consumed. Therefore, the wet gel as obtained

from the sol-gel reactions is subjected to further aging processes. During aging, the network is

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Page 14 of 96
left to grow further in the mother liquor with controlling the parameters like pH value,

temperature, and time. The aging parameters have a significant impact on the physical properties

mainly in strengthening the delicate structure of the obtained gel through Ostwald ripening,

coarsening, sintering and syneresis [58].

t
ip
As all the aerogels are processed via wet chemical synthesis routes, the wet gels must undergo an

appropriate drying process to obtain a highly porous, solid aerogel product. The liquid inside the

cr
gel structure must be removed without compromising the initial structure and dimensions.

us
Several subs- or supercritical, freeze-drying and vacuum drying approaches have been employed

to dry the wet gels to remove the liquid inside the gels. The most common and to some extent,
an
the benignest approach to dry the gel is the drying at ambient pressures after surface

modification – which is well established for silica and carbon, and, to a lesser extent
M
supercritical extraction with CO2 (scCO2) due to its easily accessible critical conditions [58].

Usually, the wet gel structure collapses upon drying due to the high capillary stresses that act on
d

the pore walls upon evaporation of a solvent. In this respect, the capillary stress can often be
e

mitigated by anchoring an appropriate non-polar moiety to the pore surface e.g. methyl moieties
pt

and exchanging the pore liquid to e.g. hexane as a low surface tension solvent thus allowing to
ce

prepare crack-free monoliths [59]. In scCO2 drying which is also called ‘’cold process’’, the pore

liquid is exchanged to supercritical CO2 and therefore, there are no longer capillary stresses in
Ac

the pores due to the disappearance of the menisci of the solvent in the pore walls at this point

[60].

The carbon (C-) aerogels, which are prepared from carbonizable polymeric aerogels, e.g.

prepared from resorcinol-formaldehyde (RF), undergo an extra processing step of

’’carbonization’’, immediately after drying. In this process, the organic aerogel is exposed to

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Page 15 of 96
high temperatures (e.g. above 600 oC) in an inert atmosphere to decompose oxygen and

hydrogen moieties of the polymeric chain, thus forming carbon networks according to synthesis

route i in Fig. 2 [61].

In the synthesis routes ii, iii, during the sol-gel process, several molecular precursors or even

t
ip
micro - or nanoparticles introduces into the reaction mixture at a single synthesis step to be

engaged in the sol-gel reaction. In these synthesis routes, the second phase will be distributed on

cr
the main network at both molecular and nanoscale level adding the extra property to the network

us
without noticeably affecting the aerogel physical properties. Taking advantage of both synthesis

routes, magnetite doped silica aerogel has been prepared by Maleki et al. [62], and Koebel et al.
an
[63] to have the mixed properties of their constituents through the addition of magnetite

nanoparticles into the prepared sol or mixing the iron salts with organosilanes along the
M
preparation of sol.
d

Additionally, deposition/ precipitation of metal hydroxides on preformed wet gels by adjusting

e

the pH of the solution, impregnation of preformed aerogel network by a solution of metal salt
pt

and, vapour phase deposition of metal particles on aerogel networks - synthesis routes iv, v and vi

respectively - were regarded as straightforward approaches to prepare multi-component catalyst

ce

supports [57].
Ac

More recently, a major breakthrough was also made in the development of oxide free and metal-

doped oxide free functional aerogels such as metal sulfides, selenides,  tellurides (chalcogenide)

by Brock et al. [64, 65] which open enormous opportunities in various applications namely

catalysis and photocatalysis. The development of pure metallic aerogel including Fe, Co, Ni, Sn,

and Cu by a carbothermal method by Leventis et al. [66-68], but also the aerogels derived from

quantum dots e.g. Au, Ag, Pt, and Pd as well as multimetallic including Au−Ag, Au−Pd, Pt−Ag,

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Page 16 of 96
Pd−Ag, Pt−Pd, Au−Ag−Pt, Au−Pt−Pd, Ag−Pt−Pd, and Au−Ag−Pt−Pd by destabilization of their

aqueous colloidal building blocks by Eychmüller et al. [69-72] were reported. Most of these

exotic aerogels have also been considered for catalytic, electrocatalytic and bioelectrocatalytic

purposes.

t
ip
3. Aerogels in air cleaning applications

cr
In the light of growing concerns regarding the ever-rising air pollution and subsequent global

us
warming, different environmental cleaning based catalysts were explored to convert the various

atmospheric organic and hazardous inorganic pollutants into less harmful compounds. In this
an
respect, the contribution of aerogel catalysts with different molecular resources has been notable

to protect and improve the environment from various hazardous pollutants. In this section, we
M
highlight the application of aerogels for catalytically and photocatalytically removal of air

pollutants.
e d
pt

3.1. DeNOx applications

Due to the harsh working conditions of the NOx abatement process, also called de-NOx, the
ce

catalyst supports that are doped with the active species must display a good activity, selectivity,
Ac

and a high thermostability. In addition, the catalyst support must have a large specific surface

area even at high reaction temperatures i.e. at 800-1200 K [73].

The selective catalytic reaction of NOx by NH3 is called SCR-NH3, and the overall reaction in

the presence of oxygen is presented according to the schematic reaction below [73]:

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Page 17 of 96
 4NO + 4NH3 + O2 4N2 + 6H2O (1)

6NO2  + 8NH3 7N2 + 12H2O        (2)

Amongst various metal oxide catalyst supports such as silica, zirconia, alumina, and titania

t
reported for SCR-NH3 of NOx; V2O5-TiO2 is recognized as the most efficient catalyst support,

ip
today [74] especially when doped in trace amount with other oxides like WO3 or MoO3 to

cr
increase activity and stability [30, 75].

us
In fact, V2O5-TiO2 obtained by conventional synthesis approach exhibits a good activity and

selectivity towards formation of N2 as well as an excellent resistance against poisoning by SOx

an
that is usually discharged from the exhaust gases of the stationary combustion sources [6, 76].

Various preparation method for vanadia-titania catalyst, such as impregnation [77], precipitation
M
[78], solid-solid wetting of TiO2, with V2O5 [79], grafting from non-aqueous solutions [77, 80]

or chemical vapour deposition [77, 81] have been studied. However, the TiO2 support is only
d

obtained with relatively lower mechanical and thermal resistance than other oxides e.g. silica,
e

and with rather low surface area. To overcome this issue, TiO2 is processed in aerogel through a
pt

sol-gel technique followed by a supercritical extraction process for drying the material. This
ce

process can lead to the formation of TiO2 catalyst aerogels with superior textural properties (e.g.

high specific surface area and porosity) as well as an excellent catalytic activity [82]. In the other
Ac

word, the advantage of aerogel catalyst arises from its high surface area which originated from

the better preservation of the porous networks thanks to the supercritical drying. As the catalytic

reactions take place on the surface, a high surface area in aerogel can, in principle, provide more

surface active sites for heterogeneous catalytic reactions. Besides, a large surface-area can better

stabilize a catalytically active phase of metal, or an oxide deposited on the surface [83].

18
 

Page 18 of 96
Almost all vanadia-titania, V2O5-TiO2, (V-T) mixed oxide aerogel catalysts have been

synthesized through either the co-condensation method starting from molecular precursors and

critical point drying (synthesis route iii - Fig. 1) or via two-step reaction of soaking a preformed

titania gel with a vanadium solution – the alkoxide precursors diluted in isopropanol (i-PrOH)  -

t
and then the resultant gels were subjected to supercritical drying and calcination at temperatures

ip
of ca. 550°C [27]. In addition, Engweiler and Baiker [82] reported V-T aerogel catalysts through

cr
chemical vapour deposition (CVD) of vanadia on the surface of preformed titania aerogel,

us
similar to the synthesis route vi - Fig. 2, or through impregnation of titania aerogels with a non-

aqueous solution using vanadyl tri-isopropoxide as a vanadium precursor, similar to the synthesis
an
route v - Fig. 2. Generally, all mentioned strategies resulted in aerogel networks having core-

shell type building blocks in which vanadia forms an outer shell to be easily involved in the
M
catalytic reactions. It is thought that the vanadyl surface species (V=O groups) are responsible

for SCR system.

d

Another reason for enhancement in the catalytic activity on V-T aerogel is due to the  good
e

dispersion of vanadium oxide on TiO2 which gives rise to the formation of ”isolated” vanadyl
pt

centers [84] and ”polymeric” polyvanadate species [85] on the surface, (cf. Fig. 3a). The
ce

semiconducting nature of TiO2 is another asset for its high catalytic activity in SCR in which the

d-orbital levels of vanadyl centers are located within its energy gap near to the conduction band.
Ac

Since 1970, several mechanisms for SCR have been investigated over vanadia-based catalysts

[30]. Busca et al. [30] gave an overview of mechanistic pathways and the chemistry beyond the

SCR-NH3 of NOx over different oxide catalysts. Surface species are known to be involved in the

reaction scheme of SCR and are identified by FTIR spectroscopy comprising molecularly

adsorbed ammonia typically as ammonium ions over Brønsted acidic -OH surface hydroxyl

19
 

Page 19 of 96
groups (Fig. 3b i), or through Lewis-type interactions on unsaturated cations (cf. Fig. 3b ii) [86].

Fig. 3c indicates one possible mechanism of SCR on the V-T catalyst supports proposed by

Janssen et al. [87] in which the intermediate species of V-ONH2 is the key element in the SCR

reaction. 

t
The catalytic performance of V-T aerogels depends on the amount of the vanadia loading and

ip
consequently increases with high vanadia loadings [74]. It has been reported that the co-gelled

cr
aerogel converted ~ 83% of NO while this value for aerogels from the two-step soaking route

us
was 66.5% [74].

an
M
e d
pt
ce
Ac

Fig. 3 (a) i) Proposed structures for monomeric vanadyl species, ii) dimeric and, iii) polymeric

metavanadate species in their dehydrated forms on the surface of V2O5-TiO2 catalysts [85, 88];

(b) i) ammonium ions bonded at V Brønsted acid sites ii) Lewis-bonded NH3 at vanadyl sites; (c)

mechanism of the NO-NH3 reaction on supported vanadium oxide catalysts proposed by Janssen

et al. [87] in the presence of oxygen.

20
 

Page 20 of 96
Baiker et al. [27] indicated that for the low-temperature (LT) SCR-NH3 of NO, vanadia grafted

on titania aerogels exhibited higher specific reaction rates (turnover frequency (TOF)) than

vanadia grafted SiO2 or vanadia grafted binary TiO2-SiO2 aerogel catalyst supports. The high

catalytic activity of the titania catalysts was attributed to the high surface area and homogeneous

t
loading with vanadia species. The low-temperature activity of V-T aerogels was significant with

ip
high loading of vanadia, i.e. ~ 6-7 μmol Vm· 2, and the catalytic activity remained constant up to

cr
620 K. In contrast, V2O5–SiO2, V2O5–TiO2–SiO2 even at higher loading of V2O5 deactivated

us
during SCR up to 620 K, due to the lower acidity of the support which was an important factor

for SCR activity. Kang et al. [89] showed that V-T aerogels could reduce up to 90% of NOx gas
an
in the presence of oxygen over a wide temperature window. Besides, high active surface area, the
M
high catalytic activity in this aerogel was attributed to the strong acidic sites as well as different

vanadyl and polymeric vanadate species on the surface.

d

The SCR catalytic activity of V-T aerogel has also been reported to increase by doping 0.1% of
e

ceria additives and has been exceeded to the maximum possible activity of ~95% by doping 1%
pt

W additive in the V-T-W ternary catalyst counterparts [76].

ce

Carbon based catalysts have also been utilized for NOx abatement in last years as they are able

to bring down the reaction temperature more than TiO2 catalytic systems with presenting higher
Ac

deNOx conversion [90].  However, carbon catalysts in the form of monoliths or membranes are

more of interest for this purpose due to the excellent and tunable physical properties [91].

The catalytic activity of carbon-based materials is correlated with both chemistry and textural

properties, and both can be deliberately controlled according to the synthesis and processing

conditions (e.g., pH of the reaction, drying procedures and carbonization temperature); allowing

21
 

Page 21 of 96
to tailor the material properties for specific applications [92-95]. Chemical functionalities on the

carbon surface, namely oxygen groups with an acid or basic behavior and presence of

heteroatoms (usually nitrogen functionalities) can be beneficial for support-active phase

interactions, thus resulting in enhanced catalytic activity of the carbon materials towards NOx

t
abatement [96, 97]. In the other hand, the textural properties also contribute to the catalytic

ip
activity, and in this case, the most important textural properties are the surface area, as the

cr
surface area determines the number of available active sites for catalytic reactions,

us
interconnected mesoporous structure and modifiable pore size distribution [98]. The carbon-

based catalyst when impregnated with different active phases of Cu [99], Fe [99, 100], Mn [101,
an
102], and V compounds [96, 103] can contribute in SCR deNOx process having low optimal

reaction temperature. The activated carbon-based catalyst containing vanadium as an active

M
phase (using coke ashes as V source) has been extensively studied by Lazaro et al. [96, 104,

105]. They found that the textural properties like surface area, porosity, and the presence of
d

surface oxygen groups can be decisive on the stable fixation of vanadium on the carbon surface.
e

The SCR-deNOx process in the presence of ammonia and O2 and vanadium supported carbon
pt

catalyst (3% wt V-load) was increased with the highest number of surface groups. In some cases
ce

surface treatment of carbon catalyst with HNO3 yielded higher NO conversion, achieving almost

90% conversion [96]. It has been reported that ammonium chemisorption on the V center of the
Ac

catalyst as well as on the oxygen functionalities (carboxylic acids moieties) was a key step in the

overall deNOx mechanism of reaction [106].

Despite the high utilization of activated carbon, carbon nanofiber and ordered mesoporous

carbon materials (OMC) [90], carbon-based aerogels or xerogels specifically has very limited

studies for the SCR-deNOx process in the literature. However, carbon xerogels have been

22
 

Page 22 of 96
contributed in NO abatement through an oxidation of NO to the higher oxidation state of NO2 at

room temperate; subsequently, the produced NO2 was captured in water as nitric acid moieties

[98]. In this context, different carbon-based xerogels have been investigated which was prepared

by the reaction of resorcinol and formaldehyde by varying the pH of the reaction, and subsequent

t
drying and calcination under various temperatures. The calcinated carbon xerogels were

ip
chemically treated on the surface with urea or oxidized with nitric acids to enhance surface

cr
active sites like nitrogen and oxygen groups with a moderate alteration in the textural properties.

us
Although the oxidative treatment has less effect on the catalytic activity, the urea treatment

enhanced the catalyst performance and increased the NO oxidation at relatively low
an
temperatures. Also, the highest catalytic oxidation of NO have been achieved with samples

contain the highest surface area (~714 m2 g-1) [98].

M

3.2. VOCs combustion

d

Volatile organic compound corresponds to the organic compounds with the low boiling point
e
pt

that causes a large amount of solvent to evaporate from a liquid state or to sublimate from the

solid state of compounds and enter to the surrounding airs with relatively high vapour pressure
ce

[107]. VOC is very toxic for both human and the environment. Therefore, their removal is an

urgent need. Catalytic combustion of VOC is recognized as the most efficient and
Ac

environmentally benign approach due to its low operation temperature (around 250–500 °C) with

less NOx formation when compared to the conventional thermal oxidation methods [108].VOC

combustion catalysts contain noble metals (Pt, Pd, Rh, Au, Ag), transition metal oxides (Ni, Cu,

Co, Cr, Ti, Fe, etc.), as well as their combinations (e.g. MnOx-CuOx, MnOx-CeO2) as nano or

microscale particles homogeneously dispersed on highly porous oxides such as carbon, alumina

23
 

Page 23 of 96
or silica [34, 109-119]. The catalytic performance of a catalyst in VOC combustion has been

determined by i) intrinsic properties of active phase (e.g. dispersion, loading, oxidation state,

etc.), ii) characteristics of support (e.g. porosity, hydrophobicity) and, 3) operating parameters

(e.g. concentrations of VOC, VOC type, flow rate, reactor type) [120].

t
ip
Catalyst based on the noble metals is more preferential and practical for combustion catalysis of

VOCs due to the high catalytic activity, resistivity to deactivation and possibility of regeneration

cr
[113, 121]. However, high costs, as well as sensitivity to the poisoning by chlorine or chloride

us
compounds, have limited their industrial applications. Instead, transition metal oxide based

catalysts display less activity while are more efficient regarding cost.
an
Aerogels, in general, are recognized as the suitable candidates for the adsorption/ absorption of
M
VOC vapours from effluents due to their tunable textural e.g. high specific surface area and

porosity and structural properties e.g. density and monolithic structures as well as tunable surface
d

chemistry [122, 123].

e

Some aerogels like carbon, transition metal oxide, and mixed oxides aerogels combined with
pt

noble metal catalysts, such as Pt, Pd, etc., have been proposed as combustion catalysts for
ce

removal of VOCs [26]. However, carbon aerogels have presented better catalytic performances

for VOCs combustion compared to the metal oxides due to the number of reasons: 1) the
Ac

hydrophobic character which allows performing VOC combustion at relatively low temperatures

with minimum water vapour chemisorption on the catalyst surface, 2) the tunable textural

properties that allow for the homogeneous and high dispersion of the active metal phase on the

support along with a good adsorption performance of the support toward VOCs [122, 123].

However, the size of porosity in carbon aerogels must be adjusted through controlling the sol-gel

24
 

Page 24 of 96
parameters, carbonization and activation conditions in such a way that metal particles retain their

catalytic activity [124].

Various methods such as impregnation, doping, equilibrium adsorption, CVD, etc. are

investigated to deposit the noble metal on carbon aerogels. Among these methods, the doping the

t
ip
initial organic solutions is recognized to be highly efficient, as the probability of sintering and

the loss of active phase by leaching is very low [125]. The important feature of metal-doped

cr
carbon aerogel is relying on its ease of preparation which is normally carried out by the addition

us
of a soluble metal salt to the initial organic mixture. After gelation, the metal ions are entrapped

inside the gel structure and chelated by the organic functional groups of the polymer matrix. The
an
entrapped metal ions inside the gel structure vary the degree of polymerization in the polymer

matrix, and as a consequence, an alteration in some textural properties in filigree aerogel i.e. pore
M
size and morphology occurs. After carbonization, the metal phase is distributed homogeneously

through the porosity of the carbon aerogel [124]. Therefore, it is expected that organic aerogels
d

greatly determine the homogeneity of metal phase distribution on carbon aerogels and textural
e

properties as a first obtained solid material.

pt

Maldonado-Hodar et al. [126] prepared platinum-containing carbon aerogels through two

ce

strategies: 1) impregnation of preformed carbon aerogels with the Pt coordination compound

[Pt(NH3)4]Cl2 (A-series catalyst) or 2) through mixing the [Pt(NH3)4]Cl2 precursors with the
Ac

initial organic monomer mixture and followed by pyrolysis to obtain carbon aerogels (B-series

catalyst). In the case of the A-series, the catalyst was pretreated with H2/ He in order to develop a

metallic Pt in a carbon matrix, while in the case of B-series, the metallic Pt were obtained during

the heat treatment of carbonization process. The toluene combustion performance of the prepared

catalysts was studied by conversion versus reaction temperature (light-off curve) and conversion

25
 

Page 25 of 96
versus reaction time at different toluene concentrations. The light-off curve in case of the A-

series catalyst indicated that the total toluene conversion shifted to lower temperatures by

increasing Pt particle sizes while in the case of B-series catalyst the reverse happened. These two

different combustion behaviors were ascribed to the difference in the dispersion pattern of Pt in

t
both catalyst series and the availability of surface active centers at certain particle sizes and

ip
encapsulation of active sites in the carbon matrix.

cr
The adsorption behavior in metal-doped carbon aerogel is varied and influenced by textural

us
properties such as micropores volume, their size distribution as well as surface chemistry and

hydrophobicity which are all controlled by the carbonization temperature [122]. In the study by
an
Maldonado-Hodar et al. [122], two series of Pt/carbon aerogels (1% Pt loaded in catalyst)

through impregnation and doping approaches were prepared. The performance of these series of
M
aerogels on both catalytic combustion and adsorption abatement of aromatic and oxygenated

VOCs were almost different and influenced by their preparation method and textural and
d

chemical properties. Increasing the carbonization temperature from 500 to 1000 °C positively
e

influences the adsorption capacity of toluene which showed the lowest polarity among the
pt

studied VOC. This was true for the static adsorption behavior of the catalysts at room
ce

temperature while in the case of dynamic adsorption condition the adsorption capacity decreased

continuously with increasing reaction temperature up to the 200°C due to the effect of
Ac

temperature on the pore size distribution of aerogels [122]. The higher the carbonization

temperature (>1000°C) the more thermally stable become the aerogels because the weaker bonds

were gasified and only the thermally robust C-C bonds remain in the solid matrix. Fig. 4

indicates the light-off curves of aerogel catalysts for the combustion of p-xylene (a) and acetone

(b). The figures are based on the VOC disappearance (Xtotal) and the CO2 conversion (XCO2) due

26
 

Page 26 of 96
to the selectivity of combustion to the CO2 formation and it is reported that CO2 + H2O are the

productions of C/Pt combustion of VOC [127]. In most cases, irrespective of the type of VOC, at

low temperature the Xtotal is greater than XCO2 which is due to the high adsorption of VOC on

carbon aerogels. As shown in Fig. 4, the total combustion of aromatic p-xylene took place at

t
relatively low temperatures (~180 °C) while in the case of acetone only 25% of VOC were

ip
destructed or converted to CO2 at this temperature. This is because of the reactivity pattern in

cr
two phases, as well as weakness in C-H bonds which vary in different VOC on the Pt/ C

us
catalysts.

an
M
e d
pt

Figure.4. Light-off curves for the combustion of (a) p-xylene and (b) acetone. 0.1 g catalyst,
ce

F=60cm3 min-1, [VOC] = 1500 ppm [122]. APtH500 are the Pt-doped carbon aerogels which
were prepared by addition of [Pt(NH3)4]Cl2 as Pt precursors to the initial polymeric solution and
carbonized in 500°C while, A500-Pt refers to the aerogel catalysts series which were prepared by
Ac

impregnation (1 wt%) of the carbon aerogels by [Pt(NH3)4]Cl2 as a precursor and followed by

carbonization in 500°C. Reprinted with permission from ref. [122].

It is noteworthy to mention that the main factor to determine the reactivity of volatile organic

compounds in oxidation catalytic reactions is the strength of C-H bonds in the compounds. On

27
 

Page 27 of 96
the supported platinum catalysts, the compounds with single C-H bonds are basically more prone

to the destruction by catalytic combustions. The reactivity of various volatile organic compounds

having different functional groups has been studied over platinum catalysts supported on a range

of (non-aerogel) inorganic supports like β-zeolite, mordenite, silica or alumina. The oxidative

t
destruction of a range of organic molecules namely alcohols, ketones, carboxylic acids,

ip
aromatics, and alkanes was assessed. The observed reactivity pattern was alcohols > aromatics >

cr
ketones > carboxylic acids > alkanes. And, as long as the volatile organic compounds are

us
involved, the adsorption also might become the main factor leading the oxidative destruction

occurs at lower temperatures [128].

an
Noble metals supported on different non-aerogels transition metals such as γ-Al2O3, SiO2, TiO2,

ZrO2, Fe2O3, CeO2, MnOx, etc. unlike to their aerogel counterparts, have been extensively
M
reported [129-133]. In most of these non-aerogel catalysts, catalytic performance has been

influenced by precursor types and eventual support characteristics such as acidic or basic
d

behavior, hydrophobicity, and porosity [123]. For instance, the acidic strength in supports such
e

as γ-Al2O3, SiO2,  ZrO2, improved the catalytic performance of their noble metal supported
pt

catalysts [134, 135]. Also, among the noble metals, Au nanoparticle has been reported for its
ce

exceptional catalytic performance for VOC combustion as it can be highly dispersed on the metal

oxides supports such as Fe2O3, Co3O4, CeO2, TiO2, and Mn2O3 [129, 136, 137]. However, in this
Ac

case, the catalytic activity of Au supported catalysts was drastically influenced by the size of Au

nanoparticles and type of support which both were controlled by the synthesis method and

processing conditions [138]. Among the oxides mentioned above, there are also few studies

concerning utilization of their aerogels such as vanadia-titania [139], chromia supported noble

28
 

Page 28 of 96
metals and transition metal oxides [26], and alumina foam coated chromia [140] for catalytic

oxidative removal of halogenated and non-halogenated VOCs.

Choi et al. [139] applied vanadia-titania aerogels for the oxidative decomposition of 1,2-

dichlorobenzene (DCB) as an example for a chlorinated aliphatic hydrocarbon which is of major

t
risk for the environment and human health. The catalytic oxidation of DCB was conducted in the

ip
temperature range of 150-600 °C with attaining 90% conversion at 450 °C without deactivation

cr
of the catalyst during 48h of operation. Also, the catalytic activity of vanadia-titania aerogel

us
remained almost constant after conducting four different oxidation cycles, and carbon oxides

were the sole product in all temperature ranges. The catalytic activity in vanadia-titania aerogels
an
was attributed to the high specific surface area, chemical homogeneity in the distribution of

mono and polyvanadate species on the catalyst surface especially when the anatase phase of
M
titania supports was used.

 
e d

3.3. Preferential oxidation (PROX) of CO

pt

An ideal catalyst for CO-PROX must be highly active, stable and selective for CO-PROX in the
ce

H2-rich gas stream and operates at lower temperature ranges [141]. Several promising catalysts

for the CO-PROX process based on supported noble metal catalysts such as Pt, Pd, Ir, Ru or Rh
Ac

[142-145], nano-gold catalysts [146-148], and metal oxides catalysts [149-151] have been

reported.

Compared to conventional catalysts which were prepared by impregnation of catalyst to an oxide

substrate, inorganic aerogels are excellent candidates for the CO-PROX as they exhibit some

desirable characteristics such as inertness, high specific surface area, mesoporosity and good

29
 

Page 29 of 96
thermal stability [152]. In this context, alumina and silica aerogels loaded with the active metals

such as platinum, cobalt, platinum-cobalt bimetallic species [152, 153] and gold nanoparticles

[154] were used for CO-PROX from an H2-riched stream. Although silica aerogel supports have

superior characteristics than alumina supports concerning their high specific surface area that

t
allows for a good dispersion of noble metal active sites without minimum interaction as well as

ip
high reducibility of metal oxide on silica as compared to that of the alumina. In the CO-PROX

cr
process, the selectivity toward CO oxidation/ removal as well as catalytic activity at lower

us
temperatures is very important which can be controlled by the catalyst preparation methods as

well as the starting materials/ precursors. For example, Kwak et al. [153] investigated the
an
catalytic performance of bimetallic Pt-Co on alumina aerogel, and xerogel catalyst supports that

were prepared in a single stage sol-gel process. They have found that a synergetic effect of
M
platinum and cobalt conferring an improved catalytic performance toward the oxidative removal

of CO. Also, the catalytic activity of the aerogel was better than that of the xerogel catalyst due
d

to the preservation of well distributed Pt-Co bimetallic active sites in the alumina structure upon
e

supercritical drying. Indeed, ambient pressure oven drying led to large shrinkages and collapse in
pt

the gel structure causing a redistribution of the active metal sites on the support and therefore
ce

leading to a nonuniformity in the catalyst. It has also been shown that PtCo-aerogels reduced the

outlet concentration of carbon monoxide to below 10 ppm in a wide temperature range of 75–
Ac

200 °C [153]. The onset temperature was lower than that in the case of PtCo-xerogel without

consumption of H2.

Choi et al. [152] also developed Pt and Co-Pt-silica aerogels by adsorption of platinum and

cobalt ions (H2PtCl6 and Co2+) on preformed wet silica gel structure through a post-synthesis

solvent exchange adsorption. The strong interaction between PtCl62- anion and cobalt cations in

30
 

Page 30 of 96
the sol state the bimetallic Pt–Co species were obtained. The distribution of active species of Pt

and Co in the aerogel structure has been influenced by the type of metal precursors and type of

used solvents. In aerogels prepared by a post gelation soaking procedure, Pt and Co tended to

agglomerate in a co-existing site as Co-Pt bimetallic species by controlling their surface charges

t
as well as using DMF aprotic solvents. DMF as a solvent stabilized the platinum ion (PtCl62-)

ip
sites and increased its affinity to link with positively charged Co species. The major role of Co in

cr
Co-Pt doped aerogels was to increase the reducibility of Pt and rendering it to become more

us
stable in its reduced state and therefore enhance the catalytic activity by shifting the CO-PROX

to the lower temperatures [152]. The resulting aerogels possess a catalytic activity for CO-PROX
an
process from H2-riched fuel in a wide temperature range of 25-300 °C.

Au nanoparticle supported metal oxides also possess an impressive catalytic performance for the
M
CO oxidation at a lower temperature when their diameters are less than 5 nm [155]. Tai et al.

[154] reported the preparation of an Au/titania-silica aerogel catalyst system and investigated its
d

catalytic performances towards CO-PROX. Au nanoparticles at a size range of ca. 2 nm were

e

distributed and entrapped on the porous amorphous structure of titania-coated silica aerogels.
pt

The Au nanoparticles (with a loading of up to 10%) were well dispersed in the catalyst and thus,
ce

no longer subjected to sintering or agglomeration. Fig. 6 (a) shows the CO conversion reactions

for different Au loaded titania-silica aerogel catalyst samples obtained from various calcination
Ac

temperatures. The catalyst containing Au loadings higher than 0.5 wt.% had a better catalytic

activity at temperatures even below room temperature. The temperature at which the conversion

was 50% (T1/2) decreased with increasing Au loading (Table 3). In fact, oxidation per catalyst

increased monotonously with increasing Au loading for the Au/ titania-silica aerogel catalyst

samples. Also, when this catalyst was subjected to a calcination process for 2 h at 973 K, not

31
 

Page 31 of 96
only its catalytic activity did not decrease, but also it was slightly more active than when it was

subjected to calcination at 673 K. This catalytic behavior will be guaranteed when the diameter

of Au nanoparticles is taken into account. Moreover, Au nanoparticles were still capable of

retaining their sizes to below 5 nm when the catalyst was subjected to the additional calcination

t
up to 10 h at 973 K and catalyst still indicated total CO conversion below 273 K [154]. Fig. 6b.

ip
cr
us
an
M
d

Fig. 6 Temperature dependence of (a) the CO conversion for the samples having Au loadings of
e

0.14 (○), 0.39 (□), 0.93 (Δ), 5.2 (◊), 9.6 (●), and 20 (+) wt.%, (b) temperature dependence of the
pt

CO conversion for 5.2 wt.% samples calcined at 673 K (◊) for 4 h and then further calcined at
ce

973 K for 2 (+) and 4 (○) h. Reprinted with permission from ref. [154].

Table 3. Average diameters of AuNPs in catalyst samples which were calcinated at high
Ac

temperatures. Adapted by permission from ref. [154].

Temperature (K) Calcination time (h) Diameter

(nm)
873 2 2.7 ± 0.52
973 2 3.6 ± 0.92
973 10 4.9 ± 1.2
1073 2 6.2± 1.4

32
 

Page 32 of 96
3.4. Methane reforming with CO2

The primary purpose of methane reforming with CO2 is to produce synthesis gas (syngas) with

high H2/ CO ratio according to the following reaction

t
CH4 + CO2 2H2 + 2CO

ip
Apart from the hydrogen production as a clean energy source, the resulting syngas can be used

cr
for the production of liquid fuels such as methanol or diesel in Fischer–Tropsch plants [156].

us
However, methane (CH4) reforming with CO2 is also considered as an efficient way to minimize

the two most problematic greenhouse gases, such as CH4 and CO2, and convert them into the
an
beneficial synthesis gas and clean energy [157, 158]. Indeed methane reforming with CO2 can

minimize the impact of large-scale CO2 emission from fossil fuel power plants and in ammonia
M
synthesis industries and in turn abate the problems with regards to the limitation in the large-

scale CO2 storage and sequestration [28].

e d

It is well known that noble metals such as Pt, Pd, Ru, as well as other transition metals like Ni
pt

and Co can be used to catalyze the above-mentioned methane reforming process [159]. The

noble metals, in general, show the highest activity and stability with respect to the deactivation
ce

due to carbon deposition on their surface [160]. However, the high costs and limited availability

of noble metals have restricted their application. From a practical point of view, other metals
Ac

such as Ni and Co and their bimetallic system [161] have been more actively investigated for

methane reforming because of their high activity and abundance although they are more prone to

deactivation caused by the coking or carbon deposition on their surface. as a result of sintering

the metal phase on the support to prepare a bigger ensemble of metal as a nucleation site for the

carbon deposition [162]. Carbon deposition or coking on the catalyst surface during CO2

33
 

Page 33 of 96
reforming of CH4 is recognized as an unavoidable phenomenon for the high C/ H ratios in this

process. Attempts in recent decades to mitigate this problematic issue are based on controlling

the catalyst preparation and structural parameters such as the specific surface area, the size of

active metal on the catalyst supports and type of catalyst support e.g. xerogel vs. aerogel [163-

t
166].

ip
Recent studies revealed that nanoparticle catalyst exhibits a better catalytic performance due to

cr
their unique morphological and physicochemical properties which lead to a high dispersion of

us
the active metal phase on the support [162, 167]. These catalysts can be prepared with a number

of methods such as impregnation, co-precipitation or sol-gel processes [168-170]. Among these

an
preparation methods, the sol-gel technique in tandem with supercritical drying has been known

as very effective because the resultant metal oxide aerogel catalysts have shown an improved
M
catalytic behavior which is due to the high dispersion of metal on the aerogel support as well as

its strong interaction with support, leading to great activities as well as low coking rates in
d

methane reforming reactions [166, 171-173].

e
pt

Osaki et al. [174] prepared monolithic nickel-alumina (NiO-Al2O3) aerogel catalysts for CO2

reforming of methane. After calcination and H2 reduction of the catalyst, the Ni-Al2O3 catalyst
ce

was obtained with a uniform distribution of Ni throughout Al2O3 by constructing Ni–O–Al

Ac

bonding. A better catalytic performance and lower probability of catalyst deactivation by coking

and metal sintering in the co-gelled mixed oxide aerogels was observed compared to a catalyst

that was obtained by a conventional impregnation method at a same loading of NiO. In addition,

an aerogel catalyst preparation by co-gelation of two different precursors allowed to tune the size

of the metal oxide particles by changing the initial Ni ion concentration in the precursor solution

in order to prevent the nucleation of the carbon in the active metal sites. In this respect, Kim et

34
 

Page 34 of 96
al. [166] optimized the metal particle size with which the high activity and low coking rate for

the Ni-alumina catalyst were obtained. They found the sol-gel technique to be the most

appropriate to optimize the metal loading content and its size on the catalyst. The evolution of

the filamentous carbon species on the catalyst surface and its subsequent deactivation were

t
attributed to the formation of the large particle sizes of Ni (>7nm) on the conventional catalyst,

ip
or Ni impregnated catalyst during preparation and additional sintering in the post-synthesis steps

cr
[166]. Whereas aerogel catalyst due to the good textural properties and high thermal stability (up

us
to 973 K) were resistant to the carbon deposition and deactivation.

On the other hand, another important parameter that strongly influenced the carbon deposition is
an
the operation mode regarding implementing a particular type of reactor e.g. a fixed-bed vs.

fluidized-bed reactor especially when the aerogel nanostructured catalyst is used [163-166].
M
Recent investigations have shown that conducting the reforming process in a fluidized-bed
d

reactor can increase the contact of the catalyst particle with gas due to the constant circulation
e

and motion of the catalyst particle and gasification of the deposited carbon. Therefore, a
pt

substantial resistance to the carbon deposition on the catalyst surface can be attained [175].

However, for aerogels, fluidizing the catalyst in the fluidized-bed reactor is not readily possible
ce

due to the strong cohesive forces between the particles, [176] and in this case implementing a
Ac

magnetic/ electric field or ultrasound assisted fluidized-bed reactor has proven to be useful [175,

177]. Hao et al. [178] improved the fluidization quality of Co/Al2O3 aerogels by introducing an

axial uniform magnetic field to the reactor. As can be seen from Fig 4. the magnetic fluidized-

bed reforming exhibited the best catalytic activity among the conventional fluidized and fixed-

bed reactors during 20 h reforming reactions. Moreover, the catalyst in the magnetic fluidized-

bed exhibited the highest initial conversions of CH4 and CO2, which were close to the

35
 

Page 35 of 96
thermodynamic equilibrium condition, although the CH4 conversion decreased slightly from

81% to 76% by increasing the operation time to 20 h (cf. Fig. 4a). Additionally, SEM

micrographs (cf. Fig. 5a-c) of catalysts after 20 h operation revealed that the morphology of

deposited carbon on the magnetically fluidized bed was entirely different, appearing as small

t
filamentous carbon species compared to the long filamentous graphitic carbon in the

ip
conventional fluidized and fixed bed reactors.

cr
Specific surface area and the density of catalyst are also necessary for the methane reforming

us
process [175, 179]. For example, in the case of Ni-Al2O3, a high fluidizing quality and a less

coking problem for aerogel catalysts were observed when compared to their xerogel
an
counterparts. As indicated in Table 1, both catalysts indicated different properties regarding Ni

crystalline size, density, specific surface area, along with their catalytic performance and
M
percentage of evolved filamentous carbon on the catalyst surface. In the case of aerogel, upon

calcination at 650 °C, Ni species were homogeneously dispersed on the Al2O3 through forming a
d

stable NiAl2O4 spinel structure while in the case of xerogel, a poorly distributed Ni having
e

isolated NiO besides NiAl2O4 spinel supported on Al2O3. The catalytic performance with regards
pt

to the conversion of methane and CO2 and selectivity toward CO and hydrogen was much better
ce

in the case of the aerogel (20 wt% Ni loading) which was attributed to the outstanding

physicochemical properties like a low density and high specific surface area in aerogel.
Ac

Table 1 physicochemical properties with the catalytic performance of Ni(20 wt %)/ Al2O3 catalysts.

Ni(20 wt %)/ Density Specific surface Ni Catalytic Carbon deposition

Al2O3 catalyst (cm3 g-1) area (m2 g-1) crystalline performance amount (wt% of

36
 

Page 36 of 96
 size (nm) (CH4)% catalyst)

Aerogel 0.05 195 9.2 ~95% (30h) 14.6

Xerogel 130 130 13.5 ~45% (30h) 26.7

t
ip
cr
us
an
M
 
Fig. 4 Conversions of CH4 (a) and CO2 (b) as a function of time on stream over the 20 wt.%
Co/Al2O3 aerogel catalyst under the three types of reactors. Reaction conditions: 973 K, 0.1 Mpa,
d

0.12 g catalyst, 150,000 ml/h g, n(CH4):n(CO2):n(N2)=1:1:1, H=320 Oe. Reprinted with

e

permission from ref. [178].

pt

Table 2. lists the different aerogel catalysts that have been used in the methane reforming process
ce

by CO2 and their respective catalytic performance in more detail.

 
Ac

37
 

Page 37 of 96
 Fig. 5 FE-SEM images of the catalysts after 20 h operation, (a) in the magnetically fluidized bed,
(b) in the fluidized bed and (c) in the fixed bed. Reprinted with permission from ref. [178].

Table 2. Aerogel catalysts used in the methane reforming by CO2 and their performances
Aerogel Operation CH4 Conversion Deactivation Remarks Ref.
catalyst mode (%) mechanism

t
NiO–La2O3– Fixed-bed • 96% at 1173 Slight carbon • Homogeneous [180]

ip
Al2O3 reactor K after 20 h deposition on distribution of bonded
reaction the catalyst Ni-ions on the support
surface • Introducing the La2O3

cr
increased the adsorptive
capacity of CO2 by
aerogels and facilitated

us
its interaction with NiO
active sites
Ni/Al2O3 Fluidized- • Depending on Limited • The aerogel catalysts [181]
bed reactor graphitic carbon
the Ni loading
(90% for a
sample with surface
an
deposited on the
exhibited high specific
surface areas, low bulk
density, small Ni
10% Ni particle sizes, strong
loading after metal- support
M
48 h reaction) interaction, high Ni
dispersion and low rate
of carbon deposition
Co-Ni Fixed-bed • Depending on Coke deposition • Synergic effects of the [171]
d

bimetallic reactor the Co/ Ni increased by lower coke formation

ratio decreasing the rate, the smaller metal
e

• (5Co/5Ni) Co/ Ni ratio particle size and

contained the stronger metal-support
pt

highest interaction of the

conversion of catalyst were achieved
79% and by higher Co/Ni ratios.
ce

remain stable
after 30 h
reaction)
Co-Al2O3 Fluidized- • CO2 Deactivation • The granulated aerogel [182]
Ac

granules bed reactor conversion due to carbon catalyst showed better

reached deposition was catalytic stability and
equilibrium not significant greater conversion of
after 6 h and in case of methane as compared to
decreased 7% granular the non-granulated
after 25 h aerogels aerogel catalyst.
operation time • Granulation improved
solid-gas contact
efficiency. 

38
 

Page 38 of 96
3.5 Photocatalysts in air cleaning

The concept of pollutant photocatalysis involves in the mineralization of organic compounds to

t
ip
convert them into CO2 and H2O by exposing the photocatalyst to UV (Vis) irradiation under

ambient temperature and pressure [183].

cr
In a heterogeneous photocatalytic process, large specific surface area to provide active sites for

us
adsorption and interfacial photoreaction events, high porosities to facilitate the mass transport of

liquid and gaseous species, and a 3-D interconnected network to provide continuous charge
an
transfer and increased light harvesting ability, are desirable [184].

Based on the fact explained above, apparently, aerogels are proper candidates for photocatalytic
M
applications [185]. For instance, native TiO2 is considered as an efficient and relatively

inexpensive and benign photocatalyst with notable photocatalytic efficiency toward degradation
d

of various air and water contaminants. However, a wide band-gap energy which only allows
e
pt

absorption of UV light, and the low surface areas have limited its efficiency in photocatalytic

reactions [186]. Processing of TiO2 into aerogel monoliths with the sol-gel process followed by
ce

supercritical drying and heat treatment, not only provides a control of the microstructural

properties to obtain high surface area and tunable nanoporosities but also generates a desired
Ac

photoactive nanocrystalline phase of TiO2 (anatase) [187-191]. Doping with other photoactive

semiconductors can modify the band gap, inhibits a fast photogenerated electron-hole (e-/h+)

recombination and improves the photoactivity of TiO2 [186, 192, 193]. On the other hand, as in

the heterogeneous catalysis, the reaction takes place on the active surface of the catalyst, the

photoactivity of TiO2 can be further enhanced if the photocatalyst adsorbs more of the targeted

39
 

Page 39 of 96
pollutants. The adsorption capacities can be strengthened when the heterogeneous photocatalysts

are processed into 3-D and free standing robust porous aerogel structures [193].

As depicted in Fig. 7, in a gas-phase photocatalysis process on an aerogel structure, several

critical steps are involved. The first step is the adsorption of VOC compounds or other organic

t
contaminant species to the porous aerogel surface which is followed by activation of its

ip
photoactive surface by UV radiation to generate electron-hole (e-/h+) pairs. Afterwards, the

cr
˖
reaction between adsorbed species on the surface and free radicals (i.e., OH ) which are

us
produced by trapped electron-hole pairs takes place in order to degrade the adsorbed species.

Finally, the degradation products are desorbed from the surface [123].
an
M
e d
pt
ce
Ac

Fig. 7 Mechanism of heterogeneous photocatalysis reaction on the aerogel structure in the gas

phase. Note: benzene is a model VOC compound, and silica-titania aerogels are model aerogel

photocatalysts.

40
 

Page 40 of 96
The processing of TiO2 into a crack-free free standing aerogel monoliths is quite an intricate

process as TiO2 monoliths tend to rapidly collapse to powders after supercritical drying due to

their meager mechanical strength [194]. For this reason, in several case studies, molecular-level

mixed TiO2-SiO2 binary aerogels, have been prepared by adjusting the rate of hydrolysis of the

t
two alkoxide precursors during the sol-gel process [194] or by impregnation of silica alcogel

ip
with titania alkoxides [195] followed by supercritical drying and heat treatment processes. TiO2-

cr
SiO2 binary aerogels show mechanical strength but are also catalytically active as well as

us
selective towards isomerization and epoxidation reactions [16] and have also indicated a

substantial photocatalytic degradation activity in both gas and liquid phases [196]. However,
an
crack formation, and non-uniform spatial distribution of titanium in these binary oxide monoliths

are a challenge especially for titania-silica aerogels with Ti/Si ratio > 0.1 [197].
M
Despite its mesoscopic pore size, large surface area and monolithic structure, pure silica aerogels

are photocatalytically inactive. The as-prepared binary silica-titania aerogels processed from CO2
d

supercritical drying are also inactive for photocatalytic oxidation of air pollutants due to their
e

amorphous structure. Only after calcination at high temperature (723 K < T < 1023 K) after CO2
pt

supercritical drying the active polymorph anatase is accessible. Another option would be to use
ce

high-temperature supercritical drying with solvents, such as ethanol or acetone, or the assembly

of preformed crystalline nanoparticles into 3D aerogel networks.

Ac

Additionally, the size of titania nanocrystalline domains is equally important and must be in the

range of average diameters of 10 nm, obtained from peak broadening of XRD, or 7 nm, obtained

from TEM micrographs [198].

The TiO2-SiO2 aerogel (Ti/Si=1) prepared via sol-gel processing and supercritical drying with

ethanol led to the formation of crystalline anatase titania nanophases which were anchored to the

41
 

Page 41 of 96
network through the creation of Si-O-Ti bonds and provided an active medium for capture and

photocatalytic oxidation of the VOC compounds such as isopropanol and trichloroethylene

[194]. 

In another study, binary titania-silica aerogels with high content and homogenously distributed

t
titanium centers and the relatively high active surface area (650 m2 g-1) have been prepared

ip
through supercritical impregnation of titanium alkoxides into a silica alcogel followed by

cr
supercritical drying and calcination processes [199]. The microscopic investigation confirmed

us
the presence of anatase (TiO2) aggregated on the catalyst surface when the supercritical solvent,

calcination temperature, impregnation and preparation parameters were properly controlled. In

an
the case of supercritical drying with ethanol as the solvent, the formation of photocatalytic active

anatase TiO2 phases resulted whereas supercritical drying with CO2 led to the formation of
M
photocatalytic inactive amorphous structures. The binary titania-silica aerogels derived from

supercritical drying with ethanol had a suitable adsorption capacity in the absence of light with a
d

proper photocatalytic performance in the presence of light for decomposition of benzene as a

e

selected VOC [200].

pt

Additionally, pore sizes and their size distribution are other important criteria in photocatalysis,
ce

as uniform pore sizes may provide higher active surface area and more active sites, which could

be attained through the sol-gel process coupled with templating approaches [193]. This has been
Ac

addressed by Yao et al. [201] with studying the effect of different mesophases of surfactant-

templated titania-silica aerogels on the photooxidation ability of VOCs and indoor air

contaminants. Additionally, the variation of the titania contents in the aerogel photoreactor has

been studied. According to this study, the binary aerogel (Ti/Si=0.75) prepared via supercritical

extraction with ethanol and with an ordered mesophase pattern and a well-defined hierarchical

42
 

Page 42 of 96
porous structure having a uniform distribution of titania in the aerogel network shows the best

performance. The titania-silica aerogel (Ti/Si=0.75) developed in this study, has demonstrated

ordered microdomains of titania with a larger pore structure which resulted in 15 times better

photooxidation activity towards airborne trichloroethylene compared to the commercial Degussa

t
P25 TiO2.

ip
Photocatalytic abatement of air NOx also offers an interesting way to remove these harmful

cr
gases with high efficiency [202]. Photodecomposition of NOx reactions are diverse and

us
classified into the several methods of photoselective reduction, photo-oxidation, and

photodecomposition [203]. Several heterogeneous catalysts based on the metal oxides including
an
V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ta, and W have been tested as a supports for TiO2

in the photo-deNOx process [204, 205]. Despite the strong promises, aerogels utilization in the
M
photo-deNOx process has not been studied much, only a few examples of xerogels out of binary

mixed oxides of TiO2-Al2O3 toward the NO oxidation have been reported, so far [206, 207].
d

In photo-oxidation of NOx, NO convert into NO3- on an appropriate photocatalyst according to

e

the following reaction [203]:

pt
ce

TiO2 + hv eCB- + hVB+ (1)

hVB+ + H 2Oads OHads + H + (2)

Ac

NO + OHads HNO 2 (3)

HNO2 + OHads NO2 + H 2O (4)

NO2 + OHads HNO3 (5)

NO + O2- NO3- (6)

2NO + O2- +3e- 2NO 2 (7)

3NO 2 + 2OH- 2NO 3- + NO + H2O (8)

43
 

Page 43 of 96
Soylu et al. [206, 207] synthesized mixed oxides of TiO2-Al2O3 through a sol-gel process and

after ambient drying and calcination, performed the photooxidation of NOx over TiO2-Al2O3

surface in order to convert NO to the higher oxidation state of NO2 and store it in the solid state

t
in the form of nitrates and nitrites. Their results suggested that alumina can be utilized as active

ip
NOx capturing sites that can eliminate the release of toxic NO2 into the atmosphere by

cr
adsorption as well as storage processes. In fact, the high surface area in Al2O3 component

us
enabled both good dispersions of the photocatalytic active TiO2 domains on the surface as well

as the formation of additional storage sites for oxidized NOx species. Several variables like TiO2
an
loading, starting precursors, calcination temperature, and formation of the crystalline phase of

TiO2 have drastically influenced the NOx photooxidation outcomes [206]. For example, in a
M
molar ratio, Ti/Al=0.5, better photocatalytic oxidation of NOx than that of commercial TiO2,

Degussa P25 and (i.e. 75% decrease in NO2 emission) with a high storage performance have
d

been achieved. Also, photocatalytic activity in crystalline forms (anatase and rutile phase) of
e

TiO2 with which the band gap fall between 3.05-3.10 ev has been reported in light of an
pt

increased calcination temperature [207].

ce

Polymer, metal oxides, and mixed metal oxide aerogels with their highly porous network

structures and good permeability have also been utilized for controlling the indoor and outdoor
Ac

air quality. These aerogels have been proposed for being used as a suitable air filter or as an air-

cleaning device to capture air viral, bacterial bioaerosols, airborne aerosols and respirable

particulates [208-212]. In this regard, Kim et al [208] used hybrid monolithic aerogel of

syndiotactic polystyrene (sPS) and polyvinylidene fluoride (PVDF) aerogels for separation of

airborne nanoparticles with high filtration efficiency. Guise et al. [213] used packed beds of

44
 

Page 44 of 96
silica aerogel microspheres and captured aerosols in size range of 20 ~ 2000 nm. In some case

studies, the airborne bioaerosols were subjected to the deactivation or killing by titanium dioxide

through a photocatalysis reaction using a photocatalyst coated on the air filters [214, 215] glass

plates [216] or using photocatalytic aerogel matrix under ultraviolet (UV) irradiation. Cao [217]

t
synthesized titania-silica aerogel monoliths (Ti/Si = 1) with a high surface area and a good

ip
permeability and tested these monoliths for capturing the airborne aerosols and bioaerosols (~

cr
0.28 µm) and studied the disinfection capability against Bacillus subtilis by taking advantage of

us
photocatalytic oxidation performance of prepared aerogels. The filtration efficiency was reported

much better than that of the aerosol filtration test (83 % vs. 32 %) because airborne virus and
an
bacteria usually have larger sizes (>0.3 µm). The subsequent disinfection tests indicated no

bacteria colonies/ spores observed on most of the agar plates having aerogels.
M

4. Catalytic applications of aerogels for removal of aqueous pollutants

e d

4.1. Advanced Oxidation Processes (AOPs)

pt

AOPs refer to the reaction with which the highly reactive species, mainly hydroxyl radicals are
ce

produced that can attack the target organic pollutants [218]. In the context of water treatment,

aerogels have been considered as an effective heterogeneous catalysis media for decontamination
Ac

of water through performing different AOP systems such as Fenton, Fenton-like, and ozonation

processes. The concept and technical feasibility of AOPs have been explained in detail in several

review papers [219, 220].

4.1.1 Fenton and Fenton-like processes

45
 

Page 45 of 96
The schematic traditional Fenton reaction and its pollutant decomposition activity are sketched in

the following reaction scheme:

Fe2+ + H2O2 Fe3+ + HO  + HO‐                   (1)

t
HO  + organic pollutants oxidation products (2)
 

ip
In the Fenton process, the catalytic activation of hydrogen peroxide by Fe2+ leads to the

cr
generation of active OH˙ radicals that can efficiently degrade organic substances, such as

us
pollutants. The oxidized products sometimes are low molecular weight and biodegradable

organic moieties, or quite often carbon dioxide, water, and other inorganics [221]. However,
an
using dissolved iron in the traditional Fenton process has caused a major restriction particularly

in the large-scale water decontamination applications due to the need to provide an acidic
M
reaction medium (e.g. pH ~ 3) as well as other drawbacks regarding difficulties in catalyst

separation and recycling. By using solid heterogeneous catalysts for the activation of H2O2, the
d

necessity of having a strict pH control is removed. Also, appropriate design of the catalyst allows
e

the process to act selectively towards the decomposition of a particular type of the contaminant
pt

[222, 223]. Moreover, most of the heterogeneous catalysts used in this process are prone to the
ce

recycling or regeneration process which can be an asset for the economic and cost efficiency of

the process. In extensive studies, it has been shown that for the generation of more active iron
Ac

ion catalysts, it is necessary to disperse (heterogenized) them in a solid inorganic matrix, such as

silica, alumina, clay, zeolites, activated carbon, carbon and other solid supports [224-229]. Sol-

gel methods and wet impregnation of aqueous iron (III) in the preformed gel have been used in

the most of these studies to disperse the iron catalysts on the solid supports. Despite the

simplicity, the wet impregnation method has major drawbacks, such as a deficient control of the

46
 

Page 46 of 96
homogeneity and morphology of iron (III) deposition as well as of the surface area of the

resulting catalyst. It has therefore been less exploited compared to the sol-gel approach [230].

Iron oxide and iron supported heterogeneous catalysts have been widely explored for the

oxidation of aqueous organic pollutants in the presence of H2O2 oxidants. However, a significant

t
ip
improvement in the catalytic performance is expected by preparing these catalysts with a

deliberately tailored micro- and a mesoporous structure having an excellent control on pore size,

cr
tortuosity and accessible of active centers as well as surface area [230].

us
Regarding this aim, Li et al. [230] developed a series of high surface area heterogeneous

catalysts from Fe/ Al binary mixed oxide aerogels and xerogels for water decontamination
an
through a facile propylene oxide-assisted sol-gel approach. The catalytic activity of the prepared
M
aerogel and xerogel materials has been investigated towards the degradation of phenol as a

model contaminant and H2O2 as the oxidant. It has been shown that tuning the synthesis
d

parameters of binary oxides, such as the ratio of Fe/ Al, and the annealing temperature has a
e

major influence on the catalyst activity. The optimum catalytic activities have been obtained at
pt

intermediate Fe/ Al ratio as the higher Fe loading led to the formation of discrete hematite phases

that are known to be catalytically inactive. Also, increasing the catalyst annealing temperature
ce

provoked an increase in the pore size of the xerogel and therefore, allowing a facilitated access
Ac

of the aqueous reactants to internal pore surface and consequently an improvement in the

catalytic activity has been observed.

Carbon materials, especially carbon aerogels which are derived from polymer-based aerogels,

have been recognized as promising catalyst support for water purifications due to their rather low

cost, high surface area, and readiness in surface modification. Additionally, their simple and

straightforward synthesis allows the addition of metal salts easily during synthesis. The metal

47
 

Page 47 of 96
ions are trapped within the polymer matrix after gelation and in many cases coordinatively

bonded to the polymer surface functionalities, e.g. by chelating interactions [125]. After

carbonization of the polymer aerogel, the metal phase is homogeneously distributed in the porous

carbon matrix yielding a metal-doped carbon aerogel catalyst. In order to explore the importance

t
of the catalyst processing methods in the oxidation of water pollutants, Ramirez et al.[231]have

ip
investigated the role of the support in the catalytic behavior of two different matrices of carbon

cr
aerogels (from resorcinol-formaldehyde) and activated carbon (from agricultural products). Both

us
carbon matrices were loaded with Fe (7 wt% loading) through a wet impregnation approach and,

have been investigated for a catalytic degradation of non-biodegradable azo-dye Orange II (OII)
an
through a Fenton-like oxidation process. The carbon aerogel showed higher activity in the

catalytic degradation of OII compared to the activated carbon, probably due to the homogeneous
M
dispersion of the iron (mainly in Fe (II) oxidation state) on the surface of the aerogel catalyst as

well as its appropriate surface chemistry that is rich in the oxygen contents. However, despite the
d

good catalytic performance of this Fe-doped carbon aerogel, leaching of iron species is an
e

important drawback at industrial scales. To diminish the metal losses from the carbon aerogel
pt

and to improve the catalytic performance, the same group have utilized two different preparation
ce

methods of impregnation and doping approaches to load the carbon aerogel support with several

transition metals such as Ni, Fe, Co [125]. In the metal-doping-based approach, corresponding
Ac

metal precursor (acetates) has been dissolved in initial polymerization solution and after

polymerization and carbonization at a temperature of 500 °C, the doped metals acted as an

integral part of the global structure of the carbon aerogel matrix with ~ 3.5 % metal loading (A-

X, X denoted the metal). In the wet impregnation approach, before the actual impregnation of the

carbon aerogels with a metal precursors, the catalyst support has undergone to a carbonization

48
 

Page 48 of 96
temperature of 500 °C and of 1000 °C for the samples M-X and AS3-X, respectively, followed

by an activation of the catalyst in a vapour stream at 900 °C to increase its surface area. Then,

both carbon supports were impregnated with an aqueous solution of metal salts, in a final metal

content of 7 wt.%, and were treated in an inert atmosphere at 300 °C for 2 h. In the case of doped

t
catalysts, ACo and ANi were mesoporous materials with significantly high surface areas, which

ip
somewhat induced the adsorption process. However, AFe was macroporous materials with lower

cr
surface area and a low leaching rate of metal catalyst

us
The catalytic performance of metal doped and impregnated aerogel samples are shown in Fig 8a-

c. In the impregnated samples, M-X, the catalytic activity of the aerogel support for the
an
degradation OII is higher in the presence of Co and Fe (Fig. 8a). Ni has inferior catalytic

performances due to its well-known inability in splitting H2O2 to OH˙.

M
In the case of AS3-Fe (Fig. 8b), the catalytic elimination rate of azo-dye Orange II (OII) has
d

been decreased due to the great extent of adsorption as a result of its high mesopore volume. The
e

inferior catalytic behavior of AS3-Co has been attributed to the greater decrease in the surface
pt

area of support upon metal addition as well as the high leaching rate of the metal from the

support. The oxidation performance of doped carbon aerogels revealed (Fig. 8c) that the
ce

elimination of pollutants in the A-Ni and A-Co were significant at the beginning of reaction due
Ac

to the adsorption effect as a consequence of the high mesoporous volume and surface area in

these samples and then proceeded with catalytic oxidation elimination. While, in the case of A-

Fe, due to the greater extent of macroporosity and a lower surface area than A-Co or A-Ni, the

OII elimination only proceeded with catalytic degradation as the higher slope of the curve

observed after adsorption process. Nevertheless, Co and Ni were rather catalytically active; Fe

49
 

Page 49 of 96
has been recognized as the most active metal with the lowest leaching rates in the doped aerogel

[125].

Overall, metal-doped carbon aerogels (especially Fe-doped ones) behaved more active as the

metal doping approach which could mitigate the metal leaching and sintering effect compared to

t
ip
the metal impregnated catalysts. Although, in this method, metal encapsulation was a drawback

and causes a decrease in catalytic behavior as a result of limited contact of the metal with the

cr
reactant in the aerogel matrix.

us
an
M
e d
pt
ce
Ac

50
 

Page 50 of 96
Fig. 8 Orange II elimination catalyzed by M (a), AS3 (b) supports and by the carbon impregnated
with Fe, Co, and Ni (T = 30 °C, pH 3, CH2O2 =6mM, Ccat = 0.2 g L-1), and (c) by doped carbons
(T = 30 °C, pH 3, CH2O2=6mM, Ccat = 0.1 g L-1). Reprinted with permission from [125].

Co-doped carbon aerogels (Co/ CA) have been prepared and employed as a heterogeneous

t
ip
catalyst for oxidation of phenol in aqueous solutions by a Fenton-like process [232]. However,

instead of using H2O2 as an oxidant, sulfate (SO4-˖) based oxidants according to Fig. 9a, b have

cr
been used which were produced through the reaction of cobalt ions with peroxymonosulfate

us
(oxone) to generate sulfate as well as hydroxyl radicals on the surface of Co/ CA catalyst. The

generated sulfate radicals decomposed the adsorbed phenol molecules on the aerogel surface to
an
carbon dioxide and water. However, the oxidation of phenol was influenced by other pollutant

competitors which were present in the solution such as chlorophenol that has a significant
M
tendency to be adsorbed on the CA catalyst. It has also been claimed that compared to the

hydroxyl radicals, sulfate radicals exhibited a higher reactivity and reaction rates towards
d

aqueous organic pollutants because the generation of sulfate radicals from Co2+/ oxons is faster
e

than the generation of hydroxyl radicals from Co2+/H2O2. Also, degradation of phenol using Co/
pt

CA heterogeneous catalyst followed a first order kinetic model with a high dependence on the
ce

reaction temperature as a 100% degradation of phenol has been significantly reduced when the

temperature increased from 25 to 40 °C (cf. Fig. 9c).

Ac

51
 

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 t
ip
cr
us
an
Fig. 9 (a) Reaction mechanism of generation of the sulfate radicals (b) Reaction mechanism of
M
heterogeneous phenol degradation on Co/CA with oxone, (c) Effect of temperature on phenol
degradation in a heterogeneous system. Reaction conditions: [Phenol] = 50 ppm, Co/CA loading
= 0.2 g/L, oxone loading = 2 g/L. Reprinted with permission from ref. [232].
e d

4.1.2 Ozonation process

pt

Ozone has also been proposed as another attractive and powerful oxidizing agent that showed a
ce

high reactivity towards mineralization of certain aqueous organic pollutants having complex

organic molecular structures under specific operational conditions [40].

Ac

The reactivity of ozone for decontamination of pollutants is described by two processes: a) direct

reaction of molecular ozone with pollutants and, b) indirect reaction through the generation of

hydroxyl radical and subsequent oxidation of contaminants. However, in both ozonation

processes, only a partial mineralization of pollutants is observed. Additionally, the low

selectivity of the process results in a large portion of OH˙ radicals to be lost in the aqueous

52
 

Page 52 of 96
solution and, the high energy demand for ozone generation further limited this process. Using

solid catalysts for ozonation processes has drawn significant attention due to the high efficiency

in ozone transformations to hydroxyl radicals. Besides, ambient operational conditions in solid

catalysts facilitate the ozonation process for real water and wastewater treatment without the

t
additional need for thermal or light energy [233]. In past decades, transition metal oxide catalysts

ip
were frequently used as ozonation catalysts [234]. However, major drawbacks associated with

cr
using micro- or nanosized metal oxide ozonation catalyst powders are the complication in their

us
separation from wastewaters which in turn causes other issues such as futility in the catalyst

regeneration causing secondary pollution especially with iron based homogeneous catalyst,

coming into sight [235]. an

To counteract these drawbacks, one efficient way is again to use heterogeneous catalysts with
M
dispersing the homogenous solid powder (e.g. metal oxide) on the matrix of an appropriate

support to facilitate the transformation of ozone to hydroxyl radicals [236]. In one way, the high
d

efficiency and ambient operational conditions in heterogeneous catalysts give a potential for
e

practical applications for industrial water treatments. On the other hand, the feasibility of solid
pt

catalysts for renewability/ recyclability is an asset without imposing further pollutions to water
ce

that homogeneous catalysts usually cause.

Ac

In recent decades, a wide variety of insoluble heterogeneous catalysts based on dispersed or

supported metal oxides, carbon-based materials, zeolites and certain microporous

aluminosilicates have emerged [40]. Carbon aerogels, in particular, are attractive catalyst

supports for ozonation processes not only for their unique structural and physical features but

due to their versatile synthetic chemistry. For the same reasons that are pointed out at the section

4.1.1., carbon aerogels have also been drastically utilized as heterogeneous catalysts in the

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Page 53 of 96
ozonation process. In fact, the liability for being easily doped with active metal catalysts either in

the initial step of the sol-gel reaction by adding metal salts to the monomer solutions or through

impregnation of preformed wet gels with a metal salt further affirmed the effectiveness of carbon

aerogels for ozonation processes. Ozonation in the surface of carbon aerogels can be performed

t
by direct oxidation of adsorbed aqueous micropollutants with molecular ozone or through the

ip
generation of hydroxyl radicals on the aerogel surface and decompose them.

cr
Sanchez-Polo et al. [235] have investigated the efficiency of Co(II)-, Mn(II)-, and Ti(IV)-doped

us
carbon aerogels for the transformation of ozone into OH˙ radicals for degradation of sodium

para-chlorobenzoate (pCBA) in drinking water. Despite minimum influences of the metal

an
loadings on the original polymer aerogels’ textural and chemical properties, only the Mn-doped

carbon aerogel showed a high activity towards the ozonation of (pCBA). This is due to the
M
greater rate of ozone transformation into OH˙ radicals and subsequent oxidation rate of pCBA at

the surface of Mn-doped carbon aerogels compared to the corresponding Co- and Ti-doped ones.
d

In addition, the capacity of ozone transformation in Mn-doped carbon aerogel was dependent on
e

the used amount of the aerogel catalyst and concentration of Mn(II) on its surface. According to
pt

the XPS analysis of Mn-doped carbon aerogels employed in the ozonation treatment of pCBA,
ce

the transformation of ozone to OH˙ radicals is proposed to occur following the schematic

reaction mechanism indicated below:

Ac

O3 + Mn2+ MnO2+ + O2 (1)

MnO2+ + H2O Mn3+ + OH + OH‐ (2)

2Mn3+ + 2H2O MnO2 + Mn2+ + 4H+ (3)

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In the above reactions, the transformation of ozone to OH˙ radicals and subsequent degradation

of pCBA are relying on the oxidation of Mn(II) to Mn(III) and Mn(IV). Apart from the oxidation

of Mn(II), the surface chemistry of carbon aerogels is equally important in the acceleration of

ozone transformations. The surface activation of carbon aerogels to produce basic groups and to

t
reduce the oxygen species on the surface with an increase in the surface electron density can

ip
accelerate the ozone transformation to OH˙ radicals for an efficient reduction of the organic

cr
pollutants.

us
In another study, nanosized copper oxide catalysts were dispersed in the mesoporous network of

carbon aerogels (CuO-Cu2O/MCA) by sol-gel processing combined with a wet impregnation

an
approach with Cu ions for catalytic ozonation of dyes at simulated wastewaters [236]. The

copper oxides were well dispersed in the amorphous structure of carbon aerogels with a size
M
range of 6-14 nm (observed by TEM). The synergetic effect of carbon aerogel supports and

copper oxide catalyst provided a durable and effective method for activation of ozone for
d

generation of more hydroxyl radicals and therefore decomposition of dyes. In this study, the
e

degradation efficiency of the catalytic ozonation process has been determined via two analytical
pt

techniques of colour removal or decolorization by recording the absorbance of the dye in the
ce

UV-Vis spectrum and COD colorimetry techniques. As indicated in Fig. 10, it has been shown

that CuO-Cu2O/MCA catalysts have a greater improvement for dye degradations concerning
Ac

colour removal rates than the ozonation process alone (Fig. 10a). Same improvements have

occurred regarding COD reduction up to 46% for catalytic ozonation while this value was only

29% for non-catalytic ozonation after 60 min treatment (Fig. 10b). Also, some experimental

variables such as increasing the ozone dosage with an enhanced pH value, reaction temperature,

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Page 55 of 96
and catalyst loading have led to a positive effect on the dye degradation rate regarding both

decolorization and COD removal techniques.

t
ip
cr
us
an
Fig. 10. Comparison of the decolorization (a) and COD removal (b) in different processes.
M
Reaction condition: T = 30 °C; pH = 5.1; ozone dosage = 4.0 mg/min; catalyst dosage = 1 g;
Cinitial RB-5 = 800 mg/L, COD initial = 625 mg/L). The error bars represent the standard
deviation of three independent experiments. Reprinted with permission from ref. [236].
e d

4.2. Photocatalysts in water cleaning

pt

Photocatalytic degradation of aqueous phase pollutants is another promising way to deal with the
ce

environmental pollution. The photocatalytic degradation of pollutants somehow can be

categorized under advanced oxidation processes which are explained above with a small
Ac

difference in the mechanism. A similar principle compared to the gas phase can be found in the

liquid-phase, as well. As shown in below schematic reactions, the light is the source of

generation of e-/h+ pairs in photocatalytically active phases and, then the subsequent hole in

contact with water generated a highly reactive species/radical which are responsible for

degradation of pollutants at the catalyst surface.

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 TiO2 + hv TiO2 + e‐ + h+ (1)

h+ + H2O H+ + OH (2)

OH‐ + h+ OH (3)

OH +  Organic pollutant

t
H2O + CO2 (4)

ip
Similar to the gas phase, when the commonly used TiO2 based materials are involved in the

cr
aqueous heterogeneous photocatalysis reaction, firstly several properties must be improved. For

us
example, apart from the mitigation of problems regarding the high band gap in TiO2 which only

allows the adsorption of UV light (comprising 5% of solar spectrum), the fast recombination of
an
e-/h+ pairs, the morphostructural properties such as specific surface area, porosity, and

crystallinity as well as surface hydrophobicity of photocatalyst are highly influential factors in

M
the liquid phase photodegradation process.

Current research efforts are focused on the preparation of more efficient and diverse
d

photocatalysts with a better photoactivity having a narrow band gap with high response to visible
e

light and good separation of e-/h+ pairs for detoxification of water from widespread pollutants
pt

[237]. Also, for practical applications of semiconductor photocatalysts in water purification, it is

ce

ideal to immobilize the nanostructured photocatalyst on a solid surface for easy recycling and

recovering [238, 239]. The ideal solid support should have a large specific surface area, open
Ac

pores with high interconnectivity for mass transport, and appropriate surface functionalities to

anchor the photoactive phases [237]. In general, aerogels are ideal photocatalytic supports due to

their peculiar properties such as large specific surface area, open porous structure, and tunable

surface chemistry that make them appealing as a support for semiconductor photocatalysts [240].

More than these, the lightweight and controlled hydrophobicity in aerogel supports make them

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Page 57 of 96
capable of floating on the water surface that not only allows them to absorb more solar radiation

but also facilitate their recovery and recycling without being lost during the repeated cycles.

In principle two approaches can be followed: a) the semiconductor itself can be processed into a

highly porous 3D aerogel network (e.g. TiO2 aerogels) or b) semiconducting nanostructures can

t
ip
be deposited on another inactive aerogel support via impregnation of one-pot sol-gel approaches.

The wet chemical synthesis is always followed by high-temperature supercritical drying or

cr
thermal treatment, In this case, the sol-gel process allows the molecular to the nano-level mixing

us
of photoactive, semiconducting elements with the support and also allows to tailor the network

from nano to micrometer lengths scale [241].

an
Although nowadays various types of aerogel supports from biomass derived carbon aerogels,
M
graphene, to polysaccharide-based aerogels are emerging [241-250], the majority of studies in

the photocatalytic water purification applications of aerogels are devoted to titania aerogels and
d

their composites with other semiconductor elements [251-253]. In addition, binary silica-titania
e

aerogels are of interest. Using the binary silica-titania aerogels is advantageous as this composite
pt

combines the large surface area/ porosity with the high adsorption capability of silica aerogels

with the semiconductor behavior of TiO2 to yield a high-performance heterogeneous

ce

photocatalyst [254]. However, still, the challenge in this area is to improve the aerogel properties
Ac

by controlling the manifold synthesis and processing conditions in order to establish a well-

understood structure-property relationship. For example, Ahmed and Attia [255] prepared silica-

titania binary photocatalyst aerogels for photodegradation of aqueous cyanide into CO2 and N2.

They have found that the high content of SiO2 increased the photodegradation efficiency as the

presence of SiO2 decreased the extent of shrinkage during drying and generated high specific

surface area, translucent and crack free aerogel monolith which can easily be handled and

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recycled several times and absorbed light efficiently. In contrast, in the study by Deng et al.

[256], the best photocatalytic activity of TiO2-SiO2 has been achieved at a molar ratio Ti: Si=1:1.

Above this molar ratio, the higher the content of SiO2, the less efficient photodegradation of

phenol was, which might be due to the fact that the high contents of SiO2 do not allow the easy

t
access of pollutants to the photoactive sites. In the study by Malinowska et al. [196] the

ip
photocatalytic activity of both pure TiO2 and TiO2-SiO2 aerogels towards different phenol para-

cr
derivatives (p-chlorophenol, p-nitrophenol, 4-hydroxybenzoic acid) were explored. The

us
photocatalytic activity of pure titania aerogels was much better than that of binary aerogels due

to the occurrence of phase separation between two phases and less likely of the creation of
an
chemical linkage of Si-O-Ti. However, Gao et al. [257] suggested a better photocatalytic activity

for binary silica-titania aerogels than that of pure titania aerogels which was ascribed for the
M
charge transfer behavior of SiO2 that can rapidly transfer the photoinduced electrons and holes to

the solution and, to the network ligands and inhibits their fast recombination.
d

Zhu et al. [258] developed ambient pressure dried, recyclable superhydrophobic silica-titania
e

aerogels for the adsorption and photocatalytic decomposition of Rhodamine B (Rh-B), a toxic
pt

organic dye, from the water. These binary aerogels show a photodegradation capability for
ce

decomposition of more than 75% of Rh-B within 100 minutes of exposing to UV light.

Moreover, the hydrophobicity of these binary aerogels has been an essential property which not
Ac

only allows the aerogel to float on water which facilitates capturing the pollutants and

accumulating them in the vicinity of active TiO2 sites, but it also allows the effective capturing

the UV light without losing the surface hydrophobicity.

Silica-titania aerogels has also recently been reported through chemical liquid deposition (in a

repeated deposition cycle 5 to 15) of prehydrolyzed titanium alkoxides (10 wt%-20 wt%) on the

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preformed silica wet gels by reaction of hydroxyl groups on the silica network with those on the

partially hydrolyzed titania in water (cf. Fig 11a) [259]. After heat treatment at 600 °C, the

typical obtained composite aerogel after 15 deposition cycles (SiO2-TiO2-15) possessed a surface

area of 425 m2 g-1 which were suitable for effective catalytic degradation of methylene blue (MB)

t
in water. As a result of repeated deposition, the growth of titania nanoparticles and titania nanocoating on

ip
silica surface have been occurred and led to the formation of silica-titania composite aerogels. Apart from

cr
the surface area in composite, the small particle size and crystallinity in titania, as well as deposition

cycle, have significantly influenced the photocatalytic performance of composites. Formation of anatase

us
TiO2 phase have been tracked by using a high-resolution TEM and with observing the clear lattice fringes

corresponding to (101) planes (cf. Fig. 11b). As shown in Fig 11c, after exposure for 100min, the
an
concentration percentages of MB with sample SiO2-TiO2-5, SiO2-TiO2-10 and SiO2-TiO2-15 were 45%,

22%, and 8% respectively [259].

M
e d
pt
ce
Ac

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Page 60 of 96
Fig. 11 (a) Schematic representation of preparation of silica-titania composite aerogels via a
chemical liquid deposition method; (b) photograph of typical aerogels SiO2-TiO2-15 treated at
600 °C with its high-resolution TEM micrograph revealing the crystalline anatase phase of TiO2;
(c) changes in MB concentration percentage over the course of the photocatalytic degradation of
MB in the presence of the different aerogels after heat treatment at 600 ˚C along with

t
photographs of MB solution before and after exposure to irradiation for 100 min: (1) MB with

ip
silica aerogel, (2) MB with SiO2-TiO2-5, (3) MB with SiO2-TiO2-10, (4) MB with SiO2-TiO2-10.
All the aerogels are heat treated at 600 ˚C for 2h and have the equal weight. Note: SiO2-TiO2-5-

cr
15 means that the SiO2-TiO2 composite was obtained with 5 to 15 repeated deposition cycles.
Reprinted with permission from ref. [259].

us
an
Recyclable silica-titania aerogel photocatalyst beads were also prepared through a simple

synthesis approach as indicated in Fig. 11a for degradation of Rh-B in the water [254]. The
M
synthesis method involved the co-condensation of titanium and silicon alkoxides in varied Ti/ Si

molar ratios. The resulting sol was extruded through a nozzle into an oil phase to rapidly get into
d

an alcogel which after washing was dried by high temperature supercritical extraction.
e

Fig. 12b shows the interconnected porous structure of TiO2-SiO2 aerogel beads in which the
pt

titania anatase crystalline phase is uniformly distributed in the silica network. Rh-B has a
ce

maximum UV absorbance at 554 nm, which decreases over time when being adsorbed by the

aerogel beads and removed from the water upon photocatalytic degradations (Fig.12c).
Ac

Approximately 80% of Rh-B was removed within 20 min of exposure to TiO2-SiO2 aerogel

beads. Moreover, after 30 min of UV light irradiation, the colour of Rh-B adsorbed on these

aerogels faded away and changed to the yellow, thus indicating an excellent photocatalytic

performance of the aerogels beads (Fig.12d).

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Page 61 of 96
 t
ip
cr
us
an
M
e d

Fig. 12 a) The schematic representation of the synthesis process of SiO2-TiO2 aerogel beads, b)
pt

SEM and TEM micrographs of SiO2-TiO2 aerogel beads, c) Time-dependent UV-vis absorption
ce

spectra of RhB solution with SiO2-TiO2 aerogel beads (Si-Ti-5). The inset is the photographs of
RhB solution before, and after the addition of SiO2-TiO2 aerogel beads, d) Photographs of RhB
adsorbed SiO2-TiO2 aerogel beads before and after 30 min UV irradiation. Reprinted with
Ac

permission from ref. [254].

Ismail et al. [260] have studied the impact of supercritical drying and heat treatment on physical

and the photodegradation properties of silica-titania aerogels for the purification of industrial

waste streams containing Cl-, S2-, NH4+ and traces of heavy metal ions. The best aerogels

regarding the photodegradation capabilities have been obtained when they were processed by

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high-temperature supercritical drying for 30 minutes period along with 5 h heat treatment. These

processing steps were necessary for the evolution of photoactive anatase crystalline phase of

titania on the aerogel structure.

Carbon based TiO2 composites are also one of the most extensively studied photocatalysts in

t
ip
waste water treatments. Carbon-TiO2 composites exist in three different structures of a TiO2-C

hybrid; carbon supported, carbon doped and carbon coated TiO2 [261], from which many

cr
different beneficial characteristics have been achieved. The cationic and anionic doping of TiO2

us
with carbon [262, 263] is reported to narrow its band gap and enhance its photocatalytic activity

in the visible range. The nanocomposite of TiO2 and other semiconductors with carbon
an
allotropes, such as carbon nanotubes and graphene [240, 264], are also reported to decrease the e-

/h+ pairs recombination, reduce the band gap and increase the pollutant absorptivity.
M
The one pot synthesis of C-TiO2 hybrid aerogel with macroporous structures (pore size up to ~
d

996 nm) and better photocatalytic properties (4.23 time) than that of the P25, a commercial TiO2
e

(Degussa Co., Ltd., Germany), towards degradation of methylene blue under UV light has been
pt

reported [241]. The high catalytic activity has been attributed to the large light absorption

capability of the hybrid aerogel as a result of light scattering and the presence of oxygen vacancy
ce

at anatase phase TiO2 nanoparticles. In fact, carbon aerogels inhibit TiO2 nanoparticles’ growth
Ac

and increase the crystallinity of TiO2 during heat treatment and suppress the TiO2 phase

transformation from photoactive anatase phase to the less photoactive rutile phase.

The photocatalytic activity of various aerogels reported in the literature for pollution abatement

of aqueous systems is compiled and summarized in Table 4.

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Page 63 of 96
Table 4. Selected list of aerogel photocatalyst for depollution of aqueous systems.

Aerogel Synthesis Properties/ Remarks Ref.

photocatalysts
Gold nanoparticles The wet gel of TiO2 obtained • Au nanoparticle (NPs) sizes [252]
(Au Nps) loaded from the sol-gel process was and concentration affected the
Titania (Au/TiO2) impregnated with Au colloidal morphostructural and crystallinity

t
solution with the size of 4-10 of resulted aerogels.

ip
nm. • Au Nps led to increase in the
crystalline zone in titania.

cr
• The higher the concentration
of gold Nps, the more
photodegradation of salicylic acid

us
under UV light was obtained.
BiOBr/reduced A one-pot hydrothermal • Excellent dye degradation [240]
graphene oxide (RGO) method using L-lysine as a performance BiOBr under visible
composite reducing agent and the cross-
linker was applied to prepare
three-dimensional RGO-based
an •
light due to charge separation
effect of RGO
High surface area with
porous network with spongy nature
M
simultaneous growing BiOBr • High stability and
nanoparticles in its network. recyclability from aqueous
solutions
d

Titania-silica A one-pot sol-gel processes in • TSAMs contained mean [265]

microspheres water in oil microemulsion diameters of about 100 µm, a
e

(TSAMs) system followed by an ambient specific surface area of 415m2/g.

pressure drying approach were • A better photocatalytic
pt

employed to prepare aerogel activity and recyclability than P25

microspheres. TiO2 for degradation of MB was
ce

achieved.
Nanocrystalline TiO2 An epoxide mediated sol-gel • Nanocrystalline TiO2 [191]
synthesis followed by super aerogels calcined at 650 ˚C has
and subcritical dryings with shown a superior photodegradation
Ac

calcination process at 400-700 ability for aqueous phenol.

˚C
Binary titania–silica A one pot sol-gel reaction by
(TiO2–SiO2) using TiOCl2 and sodium
silicate as precursors
• The photocatalytic activity
was correlated with nanocrystalline
phase and crystalline sizes.
• Aerogel has hydrophobic [266]
properties.
• Increasing the calcination
temperature up to 400 ˚C increased
the surface area.
• Photodegradation ability of

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 aerogels towards (MB) were
correlated with their
morphostructural and hydrophobic
properties as well as calcination
temperature.
Europium oxide doped Europium oxide was doped • An improved photocatalytic [251]
TiO2 (Eu-TiO2) conveniently to titania by sol- performance towards degradation

t
gel approach of salicylic acid was achieved due

ip
to
1) the prolonged separation of
electrons and holes which were

cr
facilitated by the formation of
defects (Ti3+) and oxygen

an
M
Nanoglued binary A preformed titania with an
titania-silica (TiO2– anatase phase was immobilized
SiO2) on a 3D mesoporous network
of silica obtained from sol-gel.
d
us
vacancies on the surface,
2) the ability of europium ions to
trap electrons and minimize charge
carrier recombination under UV
irradiation,
3) presence of photoactive anatase
crystalline phase.
• Aerogels contained a high- [267]
surface-area with a Ti4+ valency.
• The photogenerated
hydroxyl radicals (OH˙) in the

solution were responsible for the

oxidation of MB.
e

• The photocatalytic reaction

pt

has followed a pseudo first-order

Langmuir–Hinshelwood (L–H)
kinetic model.
ce

CeVO4/graphene Aerogels were prepared by an • CeVO4 particles were [268]

composite electrostatic-driven self- anchored uniformly on the flexible
assembly method. graphene sheets.
Ac

• The light absorption

capability of composite improved
with an effective charge transfer
from CeVO4 particles to graphene
which led to increasing in the
photodegradation ability of
composites toward MB.
• The chemical structure of
composites was stable during
several cyclic reactions.

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Cu2O/RGO composite Aerogels were synthesized
through a facile one-pot
hydrothermal method using
glucose as a reducing agent and
cross-linker.
• Aerogels were employed for [243]
aqueous methyl orange
photodegradation.
• Enhanced light absorption
capability as a result of improved
charge separation ability of
composite by RGO was achieved.

t
• Easy recycling due to the

ip
aerogel’s light weight and
hydrophobicity was obtained.
SiO2–SnO2 composite • Crystallinity and grain size [269]

cr
Tine oxide was deposited on
preformed silica gel through of SnO2 increased with thermal
a wet deposition approach. treatment at > 500 ˚C that

us
caused an improved
photocatalytic activity.
• Aerogel exhibited rich
an photoluminesce effects as a
result of defects especially for
those related to the oxygen-
M
deficient sites.
• Aerogel composite has a
proven photodegradation
performance for decomposition
d

of MB.
e

N-doped TiO2 The N-doped-TiO2 obtained • The syndiotactic polystyrene [270]

syndiotactic by a nitration process during support offers a high surface area,
pt

polystyrene hydrolysis of titanium low density, and monolithic to the

nanocomposite (Nt- alkoxide and then deposited composites.
sPS) •
ce

on the syndiotactic Photocatalytic activity

polystyrene network. toward MB under visible light was
achieved.
• A better photocatalytic
Ac

activity and recovering ability

were achieved in compared to
the N-doped-TiO2 in powdered
forms.
TiO2-Ca alginate The composite was obtained • High porosity and surface [249]
polymer fibers by dispersion of TiO2 in the area were achieved for
composite hollow alginate fiber matrix composite compared to their
through a chemical vapour non-porous fiber counterparts
deposition method. • The photodegradation

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Page 66 of 96
 toward MO for composite was
much higher (three-fold
enhancement) than that of non-
porous fiber counterparts as
well as TiO2 powder.
• The method of composite
development is easily

t
ip
upscalable.

cr
5. Conclusions and outlooks

us
This paper constitutes the first review article in last ten years which exclusively reviewed the

catalytic and photocatalytic environmental pollution abatement using various aerogel and aerogel
an
supported catalysts. The literature studied in here are indicating increasing interests over the last

few years in applications of aerogels for being used as (photo)catalysts or (photo)catalytic

M
supports for depollution of air and water media.

Based on the literature summarized in the present paper, the aerogels are basically a profitable
d

candidate for being used as a catalytic abatement media for environmental pollutants due to their
e

versatile synthesis chemistry, a sol-gel, accompanied with the supercritical drying which would
pt

allow the tailoring the material physiochemistry, textural and morphostructural properties for
ce

different catalytic reactions. A drastic enhancement in catalytic activity, selectivity, and stability

can be attributed to the combination of aerogel illustrious physical properties like high specific
Ac

surface areas accessible to reactant/product molecules, high dispersion of active species, and

strong metal or catalyst-support or metal–metal interactions. Also, thanks to the high and

homogeneous dispersion of (photo)catalytic active phase on the aerogel support, the aggregation

problem of nanoscale catalysts as a result of their high surface area to volume ratio are mitigated

and therefore a better (photo)catalytic activity by aerogel can be attained.

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Page 67 of 96
Although the current review paper only focuses on the environmental cleaning applications of

aerogel catalysts, this fascinating material has also shown fruitful performances in steam

reforming process for producing hydrogen as a clean energy source for onboard, on-demand

applications as well as chemical product synthesis. However, despite the fact that the catalytic

t
applications of aerogels are potentially immense in number and huge in impact, they are not

ip
currently commercially available due to their rather expensive processing conditions as well as

cr
the presence of other bottlenecks like low thermal resistance and delicate mechanical strength.

us
In order to pave the way for large-scale productions and applications, today, these issues are

being mitigated to some extent by using, for example, cheap inorganic salts instead of their
an
expensive alkoxide or using sustainable biomass derived sources. Moreover, safe aerogel

processing techniques i.e. replacing the supercritical CO2 drying with an ambient pressure drying
M
approach as well as taking profit of hybridization chemistry to constitute aerogel catalysts with

less mechanical and thermal performance can counter these limitations for future applications.
e d
pt

Acknowledgement
ce

Hajar Maleki acknowledges financial support by the Austrian FWF for the Lise Meitner

fellowship (project number: M2086-N34).

Ac

6. References

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[1] N. Hüsing, U. Schubert, Aerogels—Airy Materials: Chemistry, Structure, and Properties,
Angew. Chem. Int. Ed. , 37 (1998) 22-45.

[2] H. Maleki, Recent Advances in Aerogels for Environmental Remediation Applications,

Chem. Eng. J. , 300 (2016) 98-118.

t
[3] H. Maleki, L. Durães, C. A. García-González, P. del Gaudio, A. Portugal, M. Mahmoudi,

ip
Synthesis and biomedical applications of aerogels: Possibilities and challenges, Adv. Colloid
Interface Sci. , 36 (2016) 1-27.

cr
[4] M. Koebel, A. Rigacci, P. Achard, Aerogel-based thermal superinsulation: an overview, J.

us
Sol-Gel Sci. Technol. , 63 (2012) 315–339.

[5] R. Baetens, B.P. Jelle, A. Gustavsen, Aerogel insulation for building applications: A state-of-
the-art review, Energy Build., 43 (2011) 761–769.
an
[6] G.M. Pajonk, Some catalytic applications of aerogels for environmental purposes, Catal.
M
Today 52 (1999) 3-13.

[7] J. Choi, D. J. Suh, Catalytic Applications of Aerogels, Catal Surv Asia, 11 (2007) 123-133.
e d

[8] S.S. Kistler, Coherent Expanded Aerogels and Jellies, Nature, 127 (1931) 741-741.
pt

[9] H. Maleki, L. Duraes, A. Portugal, An Overview on Silica Aerogels Synthesis and Different
Mechanical Reinforcing Strategies, J. Non-Cryst. Solids, 385 (2014) 55–74.
ce

[10] S.S. Kistler, S.J. Swann, E.G. Appel, Aerogel catalysts – thoria: preparation of catalyst and
conversions of organic acids to ketones, Ind. Eng. Chem., 26 (1934) 388–391.
Ac

[11] GM. Pajonk, SJ.Tichner, Processings of the First Internationalsymposium on Aerogels, in: J.
Fricke (Ed.)Wurzburg, Germany, 1985, pp. 23-25.

[12] GM. Pajonk, Aerogel catalysts, Appl. Catal., 72 (1991) 217-266.

[13] GM. Pajonk, Catalytic aerogels, Catal. Today 35 (1997) 319-337.

69
 

Page 69 of 96
[14] R. Tleimat-Manzalji, T. Manzalji, G.M. Pajonk, Aerogels and xerogels for catalytic
applications, J. Non-Cryst. Solids 147&148 (1992) 744-747.

[15] C. Moreno-Castilla, F.J. Maldonado-Hodar, Carbon aerogels for catalysis applications: An

overview, Carbon 43 (2005) 455-465.

t
[16] M. Schneider, A. Baiker, Aerogels in Catalysis, Cat. Rev. - Sci. Eng. , 37 (1995) 515-556.

ip
[17] J. E. Amonette, J. Matyáš, Functionalized silica aerogels for gas-phase purification, sensing,

cr
and catalysis: A review, Micropor. Mesopor. Mat., (2017).

us
[18] B. C. Dunn, P. Cole, D. Covington, M. C. Webster, R. J. Pugmire, R. D. Ernst, E. M.
Eyring, N. Shah, G. P. Huffman, Silica aerogel supported catalysts for Fischer–Tropsch
synthesis, Appl. Catal., A: General, 278 (2005) 233-238.
an
[19] S. Bali, F. E. Huggins, G. P. Huffman, R. D. Ernst, R. J. Pugmire, E. M. Eyring, Iron
Aerogel and Xerogel Catalysts for Fischer−Tropsch Synthesis of Diesel Fuel, Energ. Fuels, 23
M
(2009) 14-18.

[20] D. J. Suh, Catalytic applications of composite aerogels, J. Non-Cryst. Solids 350 (2004)
d

314-319.
e

[21] M. Power, B. Hosticka, E. Black, C. Daitch, P. Norris, Aerogel as biosensors: Viral particle
pt

detection by bacteria immobolized on large pore aerogel, J. Non-Cryst. Solids, 285 (2001) 303-
ce

308.

[22] P. Buisson, C. Hernandez, M. Pierre, A. Pierre, Encapsulation of lipases in aerogels, J. Non-

Ac

Cryst. Solids 285 (2001) 295–302.

[23] M.R. Ayers, A.J. Hunt, Molecular oxygen sensors based on photoluminescent silica
aerogels, J. Non-Cryst. Solids 225 (1998) 343–347.

[24] Y.K. Li, Y.-C. Chen, K.-J. Jiang, J.-C. Wu, Y.W. Chen-Yang, Three-dimensional arrayed
amino aerogel biochips for molecular recognition of antigens, Biomaterials, 32 (2011) 7347-
7354.

70
 

Page 70 of 96
[25] J. A. Cusumano, Environmentally Sustainable Growth in the 21st Century: The Role of
Catalytic Science in Technology, J. Chem. Educ., 72 (1995) 959.

[26] H. Rotter, M.V. Landau, M. Carrera, D. Goldfarb, M. Herskowitz, High surface area
chromia aerogel efficient catalyst and catalyst support for ethylacetate combustion, Appl. Catal.
B: Environmental, 47 (2004) 111-126.

t
ip
[27] M.A. Reiche, E. Ortelli, A. Baiker, Vanadia grafted on TiO2–SiO2, TiO2 and SiO2 aerogels
Structural properties and catalytic behaviour in selective reduction of NO by NH3, Appl. Catal.

cr
B: Environmental, 23 (1999) 187-203.

us
[28] H. Bosch, F. Janssen, Formation and Control of Nitrogen Oxides, Catal. Today, 2 (1988)
369-532.
an
[29] J.N. Armor, Environmental catalysis, Appl. Catal. B, 1 (1992) 221-256.

[30] G. Busca, L. Liettib, G. Ramis, F. Berti, Chemical and mechanistic aspects of the selective
M
catalytic reduction of NOx by ammonia over oxide catalysts: A review, Appl. Catal. B:
Environment., 18 (1998) 1-36.
d

[31] X. Cheng, X. T. Bi, A review of recent advances in selective catalytic NOx reduction
e

reactor technologies, Particuology, 16 (2014) 1-18.

pt

[32] B. Guan, R. Zhan, H. Lin, Z. Huang, Review of state of the art technologies of selective
ce

catalytic reduction of NOx from diesel engine exhaust, Appl. Therm. Eng., 66 (2014) 395-414.

[33] L. Zhiming, H. Jiming, F. Lixin, L. Junhua, C. Xiangyu, Advances in catalytic removal of

Ac

NOx under lean-burn conditions, Chin. Sci. Bull., 49 (2004 ) 2231-2241.

[34] R.J. Farrauto, C.H. Bartholomew, Fundamentals of Industrial Catalytic Processes, Blackie
AcademicLondon, 1997, pp. 640-645.

[35] H. Chen, CE. Nanayakkara, VH. Grassian, Titanium dioxide photocatalysis in atmospheric
chemistry, Chem. Rev., 112 (2012) 5919-5948.

71
 

Page 71 of 96
[36] S. Kwon, M. Fan, AT. Cooper, H. Yang, Photocatalytic applications of micro- and nano-
TiO2 in environmental engineering, Crit Rev Environ Sci Technol 38 (2008) 197-226.

[37] S.W. Yao, H.P. Kuo, Photocatalytic degradation of toluene on SiO2/TiO2 photocatalyst in a
fluidized bed reactor, Procedia Engineering (The 7th World Congress on Particle Technology
(WCPT7)) 102 (2015 ) 1254 - 1260

t
ip
[38] S. Cao, H. Zhang, Y. Song, J. Zhang, H. Yang, L. Jiang, Y. Dan, Investigation of
polypyrrole/polyvinyl alcohol-titanium dioxidecomposite films for photo-catalytic applications,

cr
Appl. Surf. Sci., 342 (2015) 55-63.

us
[39] L. Qie, W. M. Chen, H. H. Xu, X. Q. Xiong, Y. Jiang, F. Zou, X. L. Hu, Y. Xin, Z. L.
Zhang, Y. H. Huang, Synthesis of Functionalized 3D Hierarchical Porous Carbon for High-
an
performance Supercapacitors, Energ. Environ. Sci. , 6 (2013) 2497-2504.

[40] D. Shahidi, R. Roy, A. Azzouz, Advances in catalytic oxidation of organic pollutants –

M
Prospects for thorough mineralization by natural clay catalysts, Appl. Catal. B: Environ, 174-175
(2015) 277-292.
d

[41] M. Niederberger, N. Pinna, Aqueous and Nonaqueous Sol-Gel Chemistry, Metal Oxide
e

Nanoparticles in Organic Solvents: Synthesis, Formation, Assembly and Application,

Springer2009.
pt

[42] A. Feinle, M.S. Elsaesser, N. Hüsing, Hierarchical Organization in Monolithic Sol–Gel

ce

Materials, in: L.K.e. al. (Ed.) Handbook of Sol-Gel Science and Technology, Springer
International Publishing Switzerland, 2016.
Ac

[43] P. H. Mutin, A. Vioux, Recent advances in the synthesis of inorganic materials via non-
hydrolytic condensation and related low temperature routes, J. Mater. Chem. A, 1 (2013) 11504–
11512.

[44] RW. Pekala, 1989.

[45] A. Feinle, M. S. Elsaesser, N. Hüsing, Sol–gel synthesis of monolithic materials with

hierarchical porosity, Chem. Soc. Rev., 45 (2016) 3377-3399.

72
 

Page 72 of 96
[46] C.A. García-González, M. Alnaief, I. Smirnova, Polysaccharide-based aerogels—Promising
biodegradable carriers for drug delivery systems, Carbohydr Polym., 86 (2011) 1425-1438.

[47] F. Quignard, R. Valentin, F. Di Renzo, Aerogel materials from marine polysaccharides,

New J. Chem., 32 (2008) 1300-1310.

t
[48] J. A. Schwarz, C. Contescu, A. Contescu, Methods for Preparation of Catalytic Materials,

ip
Chem. Rev., 95 (1995) 477-510.

cr
[49] DR. Rolison, Catalytic nanoarchitectures--the importance of nothing and the unimportance
of periodicity, Science, 299 (2003) 1698-1701.

us
[50] T.F. Baumann, A.E. Gash, G.A. Fox, J.H. Satcher Jr., L.W. Hrubesh, Handbook of Porous
Solids, Wiley-VCH, Weinheim, 2002.
an
[51] A. Feinle, N. Husing, Mixed Metal Oxide Aerogels from Tailor-Made Precursors, J. of
Supercritical Fluids, 106 (2015) 2–8.
M
[52] C Beck, T Mallat, T Bürgi, A Baiker, Nature of Active Sites in Sol–Gel TiO2–SiO2
Epoxidation Catalysts, J. Catal., 204 (2001) 428-439.
e d

[53] J.B. Miller, S.E. Rankin, E.I. Ko, Strategies in controlling the homogeneity of zirconia-silica
aerogels: effect of preparation on textural and catalytic properties, J. Catal., 148 (1994) 673-682.
pt

[54] BJ. Clapsaddle, AE. Gash, JH. Satcher, RL. Simpson, Silicon oxide in an iron(III) oxide
ce

matrix: the sol-gel synthesis and characterization of Fe-Si mixed oxide nanocomposites that
contain iron oxide as the major phase, J Non-Cryst Solids 331 (2003) 190-201.
Ac

[55] M. Schneider, U. Scharf, A. Wokaun, A. Baiker, Vanadia-Titania Aerogels: III. Influence of

Niobia on Structure and Activity for the Selective Catalytic Reduction of No by NH3, J. Catal.,
150 (1994) 284-300.

[56] J. Wang, S. Uma, K.J. Klabunde, Visible light photocatalytic activities of transition metal
oxide/silica aerogels, Micropor. Mesopor. Mater. , 75 (2004) 143-147.

73
 

Page 73 of 96
[57] A. Corrias, M. F. Casula, Aerogels Containing Metal, Alloy, and Oxide Nanoparticles
Embedded into Dielectric Matrices, in: M. A. Aegerter, N. Leventis, M. Koebel (Eds.) Aerogels
Handbook, Springer, New York, 2011, pp. 355-363.

[58] C.J. Brinker, G.W. Scherer, Sol-Gel Science, Academic Press, New York, 1990.

t
[59] DM. Smith, D. Stein, JM. Anderson, W. Ackerman, Preparation of low-density xerogels at

ip
ambient pressure J Non Cryst. Solids, 186 (1995) 104-112.

cr
[60] H. Maleki, l. durães, A. Portugal, Development of Mechanically Strong Ambient Pressure
Dried Silica Aerogels with Optimized Properties, J. Phys. Chem. C 119 (2015) 7689-7703.

us
[61] R. W. Pekala, Organic aerogels from the polycondensation of resorcinol with formaldehyde,
J. Mater. Sci., 24 (1989) 3221-3227.
an
[62] H. Maleki, L. Duraes, B. F.O. Costa, R. F. Santos, A. Portugal, Design of multifunctional
magnetic hybrid silica aerogels with improved properties, Micropor. Mesopor. Mater. , 232
M
(2016) 227-237.

[63] D. Nadargi, J. Gurav, M.A. Marioni, S. Romer, S. Matam, M.M. Koebel,

d

Methyltrimethoxysilane (MTMS)-based silica–iron oxide superhydrophobic nanocomposites, J.

e

Colloid Interface Sci. , 459 (2015) 123-126.

pt

[64] J. L. Mohanan, I. U. Arachchige, S. L. Brock, Porous Semiconductor Chalcogenide

ce

Aerogels, Science 307 (2005) 397−400.

[65] I. U. Arachchige, S. L. Brock, Sol−Gel Methods for the Assembly of Metal Chalcogenide
Ac

Quantum Dots. , Acc. Chem. Res., 40 (2007) 801−809.

[66] N. Leventis, N. Chandrasekaran, C. Sotiriou-Leventis, A. Mumtaz, Smelting in the Age of

Nano: Iron Aerogels, J. Mater. Chem., 19 (2009) 63−65.

[67] N. Leventis, N. Chandrasekaran, A.G. Sadekar, S. Mulik, C. Sotiriou-Leventis, The Effect

of Compactness on the Carbothermal Conversion of Interpenetrating Metal

74
 

Page 74 of 96
Oxide/Resorcinol−Formaldehyde Nanoparticle Networks to Porous Metals and Carbides, J.
Mater. Chem. , 20 (2010) 7456−7471.

[68] S. Mahadik-Khanolkar, S. Donthula, A.W. C. Bang, C. Sotiriou-Leventis, N. Leventis,

Polybenzoxazine Aerogels. 2. Interpenetrating Networks with Iron Oxide and the Carbothermal
Synthesis of Highly Porous Monolithic Pure Iron(0) Aerogels as Energetic Materials, Chem.

t
ip
Mater. , 26 (2014) 1318−1331.

[69] W. Liu, A.-K. Herrmann, N. C. Bigall, P. Rodriguez, D. Wen, M. Oezaslan, T. J. Schmidt,

cr
N. Gaponik, A. Eychmüller, Noble Metal Aerogels-Synthesis, Characterization, and Application

us
as Electrocatalysts, Acc. Chem. Res. , 48 (2015) 154−162.

[70] W. Liu, A.-K. Herrmann, D. Geiger, L. Borchardt, F. Simon, S. Kaskel, N. Gaponik, A.

an
Eychmüller, High-Performance Electrocatalysis on Palladium Aerogels, Angew. Chem. Int. Ed. ,
51 (2012) 5743 -5747.
M
[71] A.-K. Herrmann, P. Formanek, L. Borchardt, M. Klose, L. Giebeler, J. Eckert, S. Kaskel, N.
Gaponik, A. Eychmüller, Multimetallic Aerogels by Template-Free Self-Assembly of Au, Ag,
Pt, and Pd Nanoparticles, Chem. Mater. , 26 (2014) 1074−1083.
e d

[72] N. Gaponik, A.-K. Herrmann, A. Eychmüller, Colloidal Nanocrystal-Based Gels and

Aerogels: Material Aspects and Application Perspectives, J. Phys. Chem. Lett., 3 (2012) 8−17.
pt

[73] S. Roy, M.S. Hegde, G. Madras, Catalysis for NOx abatement, Appl. Energy, 86 (2009)
ce

2283-2297.

[74] A. Baiker, B. Handy, j. Nickl, M. Schraml-Marth, A. Wokaun, Selective catalytic reduction

Ac

of nitric oxide over vanadia grafted on titania. Influence of vanadia loading on structural and
catalytic properties of catalysts, Catal. Lett., 14 (1992) 89-99

[75] W. Shan, Hua Song, Catalysts for the selective catalytic reduction of NOx with NH3 at low
temperature, Catal. Sci. Technol., 5 (2015) 4280-4288.

[76] R.J. Willey, C-T. Wang, J B. Peri, Vanadium-titanium oxide aerogel catalysts, J. Non-Cryst.
Solids 186 (1995) 408-414.

75
 

Page 75 of 96
[77] G.C. Bond, Vanadium oxide monolayer catalysts Preparation, characterization and catalytic
activity, Appl. Catal., 71 (1991) 1-31.

[78] Y. Watanabe, M. Imanari, M. Takeuchi, S. Matsuda, S. Uno, T. Mori, F. Nakajirna,

Parametric studies of catalysts for NOx control from stationary power plants, JP 75128680, (9
October 1975).

t
ip
[79] J. Leyrer, Solid-solid wetting and formation of monolayers in supported oxide systems,
Surf. Sci 201 (1988) 603-623.

cr
[80] A. Baiker, P. Dollenmeier, M. Glinski, A. Reller, Selective catalytic reduction of nitric

us
oxide with ammonia: I. Monolayer and Multilayers of Vanadia Supported on Titania, Appl.
Catal., 35 (1987) 351-364.
an
[81] J. Nickl, D. Dutoit, A. Baiker, U. Scharf, A. Wokaun, Vanadia on titania prepared by vapour
deposition of vanadyl alkoxide: Influence of preparation variables on structure and activity for
M
the selective ca, Appl. Catal., A: General, 98 (1993) 173-193.

[82] J. Engweiler, A. Baiker, Vanadia Supported on Titania Aerogels- Morphological Properties

d

and Catalytic Behaviour in the Selective Reduction of Nitric-Oxide by Ammonia, Appl. Catal.,
e

A: General, 120 (1994) 187-205.

pt

[83] C. Hoang-Van, O. Zegaoui, P. Pichat, Vanadia–titania aerogel deNOx catalysts, J. Non-

Cryst. Solids 225 (1998 ) 157-162.
ce

[84] G. Busca, G. Centi, L. Marchetti, F. Trifirò, Chemical and spectroscopic study of the nature
of a vanadium oxide monolayer supported on a highsurface-area TiO2 anatase, Langmuir, 2
Ac

(1986) 568-577

[85] G. Busca, G. Ricchiardi, D.S.H. Sam, J.C. Volta, Spectroscopic characterization of

magnesium vanadate catalysts. Part 1.—Vibrational characterization of Mg3(VO4)2, Mg2V2O7
and MgV2O6 powders, J. Chem. Soc., Faraday Trans., 90 (1994) 1161-1170.

[86] G. Busca, H. Saussey, O. Saur, J.C. Lavalley, V. Lorenzelli, FT-IR characterization of the
surface acidity of different TiO2 anatase preparations, Appl. Catal,, 14 (1985) 245-260

76
 

Page 76 of 96
[87] F.J. J. G. Janssen, F. M. G. Van den Kerkhof, H. Bosch, J.R.H. Ross, Mechanism of the
reaction of nitric oxide, ammonia, and oxygen over vanadia catalysts. 2. Isotopic transient
studies with oxygen-18 and nitrogen-15, J. Phys. Chem., 91 (1987) 6633-6638.

[88] I. Giakoumelou, C. Fountzoula, C. Kordulis, S. Boghosian, Molecular structure and

catalytic activity of V2O5/TiO2 catalysts for the SCR of NO by NH3: In situ Raman spectra in

t
ip
the presence of O2, NH3, NO, H2, H2O, and SO2, J. Catal., 239 (2006) 1-12.

[89] M. Kang, J. Choi, Y. Tae Kim, E. Duck Park, C. Burm Shin, D.J. Suh, J. Eui Yie, Effects of

cr
preparation methods for V2O5-TiO2 aerogel catalysts on the selective catalytic reduction of NO

us
with NH3, Korean J. Chem. Eng., 26 (2009) 884-889

[90] M. J. Lazaro, S. Ascaso, S. P. Rodriguez, J. C. Calderon, M. E. Galvez, a. J. Nieto, R.

an
Moliner, A. Boyano, D. Sebastian, C. Alegre, L. Calvillo, V. Celorrio, Carbon-based catalysts:
Synthesis and applications, C. R. Chimie 18 (2015) 1229-1241.
M
[91] N. Mahata, A.R. Silva, M.F.R. Pereira, C. Freire, B. Castro, J.L. Figueiredo, Anchoring of a
[Mn(salen)Cl] complex onto mesoporous carbon xerogels, J. Colloid Interf. Sci. , 311 (2007)
152-158.
e d

[92] A.M. ElKhatat, S.A. Al-Muhtaseb, Advances in Tailoring Resorcinol-Formaldehyde

Organic and Carbon Gels, Adv. Mater., 23 (2011) 2887-2903.
pt

[93] S.A. Al-Muhtaseb, J.A. Ritter, Preparation and Properties of Resorcinol-Formaldehyde

ce

Organic and Carbon Gels, Adv. Mater. , 15 (2003) 101-114.

[94] N. Job, A. Théry, P. René, J. Marien, J.L. Kocon, J.-N. Rouzaud, F. Béguin, J.-P. Pirard,
Ac

Carbon aerogels, cryogels and xerogels: Influence of the drying method on the textural properties
of porous carbon materials, Carbon 43 (2005) 2481-2494.

[95] L. Zubizarreta, A. Arenillas, J.-P. Pirard, J.J. Pis, N. Job, Tailoring the textural properties of
activated carbon xerogels by chemical activation with KOH. , Micropor. Mesopor. Mat. , 115
(2008) 480-490.

77
 

Page 77 of 96
[96] M.E.Gálvez, M.J.Lázaro, R.Moliner, Novel activated carbon-based catalyst for the selective
catalytic reduction of nitrogen oxide, Catal. Today, 102-103 (2005) 142-147.

[97] H. Teng, Y.-T. Tu, Y.-C. Lai, C.-C. Lin, Reduction of NO with NH3 over carbon catalysts:
The effects of treating carbon with H2SO4 and HNO3, Carbon 39, (2001) 575-582.

t
[98] J. P. S. Sousa, M. F. R. Pereira, J.L. Figueiredo, Carbon Xerogel Catalyst for NO Oxidation,

ip
Catalysts 2(2012) 447-465.

cr
[99] K. Kaneko, Z. Wang, T. Suzuki, S. Ozeki, N. Kosugi, H. Kuroda, Micropore filling of
supercritical NO on Cu-doped iron oxide dispersed activated carbon fibers, J. Colloid Interf.

us
Sci., 142 (1991) 489-496.

[100] M. Yosikawa, A. Yasutake, I. Mochida, Low-temperature selective catalytic reduction of

an
NOx by metal oxides supported on active carbon fibers, Appl. Catal. A: Gen., 173 (1998) 239-
245.
M
[101] G. Marbán, A. B. Fuertes, Low-temperature SCR of NOx with NH3 over Nomex™
rejects-based activated carbon fibre composite-supported manganese oxides: Part I. Effect of pre-
d

conditioning of the carbonaceous support, Appl. Catal. B: Environ., 34 (2001) 43-53.

e

[102] G. Marbán, A.B. Fuertes, Low-temperature SCR of NOx with NH3 over Nomex™ rejects-
pt

based activated carbon fibre composite-supported manganese oxides: Part II. Effect of
procedures for impregnation and active phase formation, Appl. Catal. B: Environ., 34 (2001) 55-
ce

71.

[103] Z. Zhu, Z. Liu, S. Liu, H. Niu, Catalytic NO reduction with ammonia at low temperatures
Ac

on V2O5/AC catalysts: effect of metal oxides addition and SO2, Appl. Catal. B: Environ., 30
(2001) 267-276.

[104] M.J. Lazaro, A. Boyano, M.E. Galvez, M.T. Izquierdo, E. Garcı´a-Bordeje, C. Ruiz, R.
Juan, R. Moliner, Novel carbon based catalysts for the reduction of NO: Influence of support
precursors and active phase loading, Catal. Today 137 (2008) 215-221.

78
 

Page 78 of 96
[105] M.J. Lazaro, M.E. Galvez, C. Ruiz, R. Juan, R. Moliner, Vanadium loaded carbon-based
catalysts for the reduction of nitric oxide, Appl. Catal. B: Environ., 68 (2006) 130-138.

[106] R.D.Vidic, C.H.Tessmer, L.J.Uranowski, Impact of surface properties of activated carbons

on oxidative coupling of phenolic compounds, Carbon 35, (1997) 1349-1359.

t
[107] A. Berenjian, N. Chan, H.J. Malmiri, Volatile Organic Compounds removal methods: A

ip
review, Am. J. Biochem. Biotechnol. , 8 (2012) 220-229.

cr
[108] F. IKhan, A. Ghoshal, Removal of Volatile Organic Compounds from polluted air, Journal
of Loss Prevention in the Process Industries, 13 (2000) 527-545.

us
[109] E. Noordally, J.R. Richmond, S.F. Tahir, Destruction of volatile organic compounds by
catalytic oxidation, Catal. Today 17 (1993) 359-366.
an
[110] P. Papaefthimiou, T. Ioannides, XE. Verykios, Combustion of non-halogenated volatile
organic compounds over group VIII metal catalysts, Appl. Catal. B: Environmental, 13 (1997)
M
175-184.

[111] P.-O. Larsson, A. Andersson, Oxides of copper, ceria promoted copper, manganese and
d

copper manganese on Al2O3 for the combustion of CO, ethyl acetate and ethanol, Appl. Catal.
e

B: Environmental, 24 (2000) 175-192.

pt

[112] C.M. Pradier, F. Rodrigues, P. Marcus, M.V. Landau, M.L. Kaliya, A. Gutman, M.
Herskowitz, Supported chromia catalysts for oxidation of organic compounds: The state of
ce

chromia phase and catalytic performance, Appl. Catal. B: Environmental, 27 (2000) 73–85.
Ac

[113] J.J. Spivey, Complete catalytic oxidation of volatile organics, Ind. Eng. Chem. Res., 26
(1987) 2165-2180.

[114] T. García, B. Solsona, S.H. Taylor, Naphthalene total oxidation over metal oxide catalysts,
Appl. Catal. B 66 (2006) 92-99.

[115] S.C. Kim, C.Y. Park, The complete oxidation of a volatile organic compound (toluene)
over supported metal oxide catalysts, Res. Chem. Intermediates 28 (2002) 441-449.

79
 

Page 79 of 96
[116] D. Kulkarni, I.E. Wachs, Isopropanol oxidation by pure metal oxide catalysts: Number of
active surface sites and turnover frequencies, Appl. Catal. A 237 (2002) 121-137.

[117] W.B. Li, W.B. Chu, M. Zhuang, J. Hua, Catalytic oxidation of toluene on Mn-containing
mixed oxides prepared in reverse microemulsions, Catal. Today 93-95 (2004) 205-209.

t
[118] B.P. Barbero, L. Costa-Almeida, O. Sanz, M.R. Morales, L.E. Cadus, M. Montes, Wash

ip
coating of metallic monoliths with a MnCu catalyst for catalytic combustion of volatile organic
compounds, Chem. Eng. J., 139 (2008) 430-435.

cr
[119] C. Hu, Q. Zhu, Z. Jiang, Nanosized CuO-ZrxCe1-xOy aerogel catalysts prepared by

us
ethanol supercritical drying for catalytic deep oxidation of benzene, Powder Technol. , 194
(2009) 109-114.
an
[120] L.F. Liotta, Catalytic oxidation of volatile organic compounds on supported noble metals,
Appl. Catal. B 100 (2010) 403-412.
M
[121] P. Papaefthimiou, T. Ioannides, X. E. Verykios, Performance of doped Pt/TiO2 (W6+)
catalysts for combustion of volatile organic compounds (VOCS), Appl. Catal. B 15 (1998) 75-
d

92.
e

[122] F. J. Maldonado-Hódar, Removing aromatic and oxygenated VOCs from polluted air
pt

stream using Pt–carbon aerogels: Assessment of their performance as adsorbents and combustion
catalysts, J Hazard Mater, 194 (2011) 216-222.
ce

[123] S. Morales-Torres, F. Carrasco-Marín, A. F. Pérez-Cadenas, F. J. Maldonado-Hódar,

Coupling Noble Metals and Carbon Supports in the Development of Combustion Catalysts for
Ac

the Abatement of BTX Compounds in Air Streams, Catalysts, 5 (2015) 774-799.

[124] C. Moreno-Castilla, F.J. Maldonado-Hódar, A.F. Pérez-Cadenas, Physicochemical surface

properties of Fe, Co, Ni, and Cu-doped monolithic organic aerogels, Langmuir, 19 (2003) 5650-
5655.

80
 

Page 80 of 96
[125] F. Duarte, F.J. Maldonado-Hódar, A.F. Pérez-Cadenas, L.M. Madeira, Fenton-like
degradation of azo-dye Orange II catalyzed by transition metals on carbon aerogels, Appl. Catal.
B: Environment., 85 (2009) 139-147.

[126] F.J. Maldonado-Hódar, C. Moreno-Castilla, A.F. Pérez-Cadenas, Catalytic combustion of

toluene on platinum-containing monolithic carbon aerogels, Appl. Catal. B: Environmental, 54

t
ip
(2004) 217-224.

[127] S. Morales-Torres, A.F. Pérez-Cadenas, F. Kapteijn, F. Carrasco-Marín, F.J. Maldonado-

cr
Hódar, J.A. Moulijn, Palladium and platinum catalysts supported on carbon nanofiber coated

us
monoliths for low-temperature combustion of BTX, Appl. Catal. B 89 (2009) 411-419.

[128] A. O’Malley, B.K. Hodnett, The influence of volatile organic compound structure on
an
conditions required for total oxidation, Catal. Today 54 (1999) 31-38.

[129] S.A.C. Carabineiro, X. Chen, O. Martynyuk, N. Bogdanchikova, M. Avalos-Borja, A.

M
Pestryakov, P.B. Tavares, J.J.M. Órfão, M.F.R. Pereira, J.L. Figueiredo, Gold supported on
metal oxides for volatile organic compounds total oxidation, Catal. Today 244 (2015) 103-114.
d

[130] A.A. Dos Santos, K.M.N. Lima, R.T. Figueiredo, S.M.D.S. Egues, A.L.D. Ramos, Toluene
e

deep oxidation over noble metals, Copper and Vanadium Oxides, Catal. Lett. , 114 (2007) 59-63.
pt

[131] V.P. Santos, S.A.C. Carabineiro, P.B. Tavares, M.F.R. Pereira, J.J.M. Órfão, J.L.
Figueiredo, Oxidation of CO, ethanol and toluene over TiO2 supported noble metal catalysts,
ce

Appl. Catal. B, 99 (2010) 198-205.

[132] L.S. Escandón, S. Ordóñez, A. Vega, F.V. Díez, Sulphur poisoning of palladium catalysts
Ac

used for methane combustion: Effect of the support, J. Hazard. Mater. , 153 (2008) 742-750.

[133] D.P. Debecker, B. Farin, E.M. Gaigneaux, C. Sanchez, C. Sassoye, Total oxidation of
propane with a nano-RuO2/TiO2 catalyst, Appl. Catal. A 481 (2014) 11-18.

[134] Y. Yazawa, N. Takagi, H. Yoshida, S.-i. Komai, A. Satsuma, T. Tanaka, S. Yoshida, T.

Hattori, The support effect on propane combustion over platinum catalyst: Control of the

81
 

Page 81 of 96
oxidation-resistance of platinum by the acid strength of support materials, Appl. Catal. A, 233
(2002) 103-112.

[135] Y. Yazawa, H. Yoshida, N. Takagi, S.-i. Komai, A. Satsuma, T. Hattori, Acid Strength of
Support Materials as a Factor Controlling Oxidation State of Palladium Catalyst for Propane
Combustion. , J. Catal. , 187 (1999) 15-23.

t
ip
[136] H. Huang, Y. Xu, Q. Fenga, D. Y. C. Leung, Low temperature catalytic oxidation of
volatile organic compounds: a review, Catal. Sci. Technol., 5 (2015) 2649-2669

cr
[137] K.J. Kim, S.I. Boo, H.G. Ahn, Preparation and characterization of the bimetallic Pt-

us
Au/ZnO/Al2O3 catalysts: Influence of Pt-Au molar ratio on the catalytic activity for toluene
oxidation, J. Ind. Eng. Chem. Commun., 15 (2009) 92-97.
an
[138] M. Haruta, Size- and support-dependency in the catalysis of gold, Catal. Today 36 (1997)
153-166.
M
[139] J. Choi, C.B. Shin, T.-J. Park, D. J. Suh, Characteristics of vanadia–titania aerogel
catalysts for oxidative destruction of 1,2-dichlorobenzene, Appl. Catal., A: General, 311 (2006)
d

105-111.
e

[140] M. V. Landau, G. E. Shter, L. Titelman, V. Gelman, H. Rotter, G. S. Grader, M.

pt

Herskowitz, Alumina Foam Coated with Nanostructured Chromia Aerogel: Efficient Catalytic
Material for Complete Combustion of Chlorinated VOC, Ind. Eng. Chem. Res. , 45 (2006) 7462-
ce

7469.

[141] A. Mishra, R. Prasad, A Review on Preferential Oxidation of Carbon Monoxide in

Ac

Hydrogen Rich Gases, BCREC, 6 (2011) 1 - 14.

[142] P.C. Hulteberg, J.G.M. Brandin, F.A. Silversand, M. Lundberg, Preferential oxidation of
carbon monoxide on mounted and unmounted noble-metal catalysts in hydrogen-rich streams,
Int. J. Hydrogen Energy Fuels, 30 (2005) 1235-1242.

[143] Y. Y. Huang, A. A. Wang, X. X. Wang, T. T. Zhang, Preferential oxidation of CO under

excess H2 conditions over iridium catalysts, Int. J. Hydrogen Energy 32 (2007) 3880-3886.

82
 

Page 82 of 96
[144] K.H. Kim, E.D. Park, H.C. Lee, D. Lee, Selective CO removal in a H2-rich stream over
supported Ru catalysts for the polymer electrolyte membrane fuel cell (PEMFC), Appl. Catal. A:
general, 366 (2009) 363-369.

[145] M-C. Jo, G-H. Kwon, W. Li, A. M. Lane, Preparation and characteristics of pretreated
Pt/alumina catalysts for the preferential oxidation of carbon monoxide, J. Ind. Eng. Chem., 15

t
ip
(2009) 336-341.

[146] L.H. Chang, Y.L. Yeh, Y.W. Chen, Preferential oxidation of CO in hydrogen stream over

cr
nano-gold catalysts prepared by photodeposition method, Int. J. Hydrogen Energy 33 (2008)

us
1965-1974.

[147] E. Quinet, L. Piccolo, H. Daly, F.C. Meunier, F. Morfin, A. Valcarcel, F. Diehl, P.

an
Avenier, V. Caps, J-L. Rousset, H2-induced promotion of CO oxidation over unsupported gold,
Catal. Today 138 (2008) 43-49.
M
[148] Y-F. Yang, P. Sangeetha, Y-W. Chen, Au/TiO2 catalysts prepared by photo-deposition
method for selective CO oxidation in H2 stream, Int. J. Hydrogen Energy, 34 (2009) 8912-8920.
d

[149] F. Marino, C. Descorme, D. Duprez, Supported base metal catalysts for the preferential
e

oxidation of carbon monoxide in the presence of excess hydrogen (PROX), Appl Catal. B:
enviromental, 58 (2005) 75-183.
pt

[150] V. Ramaswamy, S. Malwadkar, S. Chilukuri, Cu-Ce mixed oxides supported on Al-

ce

pillared clay: Effect of method of preparation on catalytic activity in the preferential oxidation of
carbon monoxide, Appl. Catal. B: environ 84 (2008.) 21-29.
Ac

[151] G. Avgouropoulos, T. Ioannides, H. Matralis, Influence of the preparation method on the

performance of CuO-CeO2 catalysts for the selective oxidation of CO, Appl. Catal. B: environ
56 (2005) 87-93.

[152] J. Choi, C. B. Shin, D. Jin Suh, Co-promoted Pt catalysts supported on silica aerogel for
preferential oxidation of CO, Catal. Commun., 9 (2008) 880-885.

83
 

Page 83 of 96
[153] C. Kwak, T.-J. Park, D. J. Suh, Preferential oxidation of carbon monoxide in hydrogen-rich
gas over platinum–cobalt–alumina aerogel catalysts, Chem. Eng. Sci., 60 (2005) 1211-1217.

[154] Y. Tai , K. Tajiri, Preparation, thermal stability, and CO oxidation activity of highly loaded
Au/titania-coated silica aerogel catalysts, Appl. Catal., A: General, 342 (2008) 113-118.

t
[155] M. Haruta, When Gold Is Not Noble: Catalysis by Nanoparticles, Chem. Rec., 3 (2003)

ip
75-87

cr
[156] J. Yang, W. Ma, D. Chen, A. Holmen, B. H. Davis, Fischer–Tropsch synthesis: A review
of the effect of CO conversion on methane selectivity, Appl. Catal., A: General, 470 (2014) 250-

us
260.

[157] Y.H. Hu, E. Ruckenstein, Binary MgO-Based solid solution catalyst for methane
an
conversion to syngas, Catal. Rev., 44 (2002. ) 423-453.

[158] B.Q. Xu, J.M. Wei, H.Y. Wang, K.Q. Sun, Q.M. Zhu, Nano-MgO: Novel Preparation and
M
Application as Support of Ni Catalyst for CO2 Reforming of Methane, Catal. Today 68 (2001)
217-225.
d

[159] J. Zhang, H. Wang, A. K. Dalai, Development of stable bimetallic catalysts for carbon
e

dioxide reforming of methane, J. Catal., 249 (2007) 300-310.

pt

[160] L. De Rogatis, T. Montini, A. Cognigni, L. Olivi, P. Fornasiero, Methane partial oxidation

ce

on NiCu-based catalysts, Catal. Today 145 (2009) 176-185.

[161] S. De, J. Zhang, R. Luque, N. Yan, Ni-based bimetallic heterogeneous catalysts for energy
Ac

and environmental applications, Energy Environ. Sci., 9 (2016) 3314-3347.

[162] J-H. Kim, DJ. Suh, T-J. Park, K-L. Kim, Effect of metal particle size on coking during
CO2 reforming of CH4 over Ni-alumina aerogel catalysts, Appl. Catal. A 197 (2000) 191-200.

[163] S. Therdthianwong, C. Siangchin, A. Therdthianwong, Improvement of coke resistance of

Ni/Al2O3 catalyst in CH4/ CO2 reforming by ZrO2 addition, Fuel Process. Technol., 89 (2008)
160-168.

84
 

Page 84 of 96
[164] H.T. Jiang, H.Q. Li, H.B.Xu, Y.Zhang, Preparation ofNi/MgxTi1−xO catalysts and
investigation on their stability in tri-reforming of methane, Fuel Process. Technol., 88 (2007)
988-995.

[165] M.A. Goula, A.A. Lemonidou, A.M. Efstathiou, Characterization of carbonaceous species
formed during reforming of CH4 with CO2 over Ni/CaO-Al2O3 catalysts studied by various

t
ip
transient techniques, J. Catal., 161 (1996) 626-640.

[166] J.-H. Kim, D.J. Suh, T.-J. Park, K.-L. Kim, Effect of metal particle size on coking during

cr
CO2 reforming of CH4 over Ni-alumina aerogel catalysts, Appl. Catal., A: General, 197 (2000)

us
191-200.

[167] M. Inoue, K. Sato, T. Nakamura, T. Inui, Glycothermal synthesis of zirconiaerare earth

oxide solid solutions, Catal. Lett., 65 (2000) 79-83.an
[168] M. C. J. Bradford, M.A. Vannice, Catalytic reforming of methane with carbon dioxide
M
over nickel catalysts I. Catalyst characterization and activity, Appl. Catal. A, 142 (1996) 73-96.

[169] J.A. Montoya, E. Romero-Pascual, C. Gimon, P. Del Angel, A. Monzón, Methane

d

reforming with CO2 over Ni/ZrO2–CeO2 catalysts prepared by sol–gel, Catal. Today 63 (2000)
e

71-85.
pt

[170] Y.-G. Chen, K. Tomishige, K. Yokoyama, K. Fujimoto, Catalytic Performance and

Catalyst Structure of Nickel–Magnesia Catalysts for CO2 Reforming of Methane, J. Catal., 184
ce

(1999) 479-490.

[171] L. Chen, Q. Zhu, R. Wu, Effect of Co–Ni ratio on the activity and stability of Co–Ni
Ac

bimetallic aerogel catalyst for methane Oxy-CO2 reforming, Int. J. Hydrogen Energy, 36 (2011)
2128-2136.

[172] H. Li, H. Xu, J. Wang, Methane reforming with CO2 to syngas over CeO2-promoted
Ni/Al2O3-ZrO2 catalysts prepared via a direct sol-gel process, J. Nat. Gas Chem., 20 (2011) 1-8.

[173] T. Osaki, T. Tanaka, T. Horiuchi, T. Sugiyama, K. Suzuki, T. Mori, Application of NiO–

Al2O3 aerogels to the CO2-reforming of CH4, Appl. Organomet. Chem., 14 (2000) 789-793.

85
 

Page 85 of 96
[174] T. Osaki, T. Horiuchi, T. Sugiyama, K. Suzuki, T. Mori, Catalysis of NiO–Al2O3 aerogels
for the CO2-reforming of CH4, Catal. Lett., 52 (1998) 171-180.

[175] Z. Hao, Q. Zhu, Z. Lei, H. Li, CH4-CO2 reforming over Ni/Al2O3 aerogel catalysts in a
fluidized bed reactor, Powder Tech. , 182 (2008) 474-479.

t
[176] F. Wang, J. Zhu, J.M. Beeckmans, Pressure Gradient and Particle Adhesion in the

ip
Pneumatic Transport of Cohesive Fine Powders, Int. J. Multiphase Flow, 26 (2000) 245-265.

cr
[177] X. Tao, M. Bai, X. Li, H. Long, S. Shang, Y. Yin, X. Dai, CH4–CO2 reforming by plasma
– challenges and opportunities, Prog. Energy Combust. Sci, 37 (2011) 113-124.

us
[178] Z. Hao, Q. Zhu, Z. Jiang, H. Li, Fluidization characteristics of aerogel Co/Al2O3 catalyst
in a magnetic fluidized bed and its application to CH4–CO2 reforming, Powder Technol., 183
(2008) 46-52.
an
[179] Z. Jiang, X. Liao, Y. Zhao, Comparative study of the dry reforming of methane on
M
fluidised aerogel and xerogel Ni-Al2O3 catalysts, Appl. Petrochem. Res., 3 (2013) 91–99.

[180] Z. Xu, Y. Li, J. Zhang, L. Chang, R. Zhou, Z. Duan, Ultrafine NiO–La2O3–Al2O3

d

aerogel: a promising catalyst for CH4/CO2 reforming, Appl. Catal., A: General, 213 (2001) 65-
e

71.
pt

[181] Z. Hao, Q. Zhu, Z. Jiang, B. Hou, H. Li, Characterization of aerogel Ni/Al2O3 catalysts
ce

and investigation on their stability for CH4-CO2 reforming in a fluidized bed, Fuel Process.
Technol., 90 (2009) 113-121.
Ac

[182] P. Li, J. Li, Q. Zhu, L. Cui, H. Li, Effect of granulation on the activity and stability of a
Co–Al2O3 aerogel catalyst in a fluidized-bed reactor for CH4–CO2 reforming, RSC Adv., 3
(2013) 8939–8946.

[183] J.M. Coronado, A.J. Maira, J.C. Conesa, K.L. Yeung, V. Augugliaro, J. Soria, EPR Study
of the Surface Characteristics of Nanostructured TiO2 under UV Irradiation, Langmuir, 17
(2001) 5368-5374.

86
 

Page 86 of 96
[184] D.T. Horvath, Synthesis, Characterization, and Photocatalytic Testing of Titania-Based
Aerogels for the Degradation of Volatile Organic Compounds, University of Connecticut, 2012.

[185] Y.-C. Chiang, W.-Y. Cheng, S.-Y. Lu, Titania Aerogels as a Superior Mesoporous
Structure for Photoanodes of Dye-Sensitized Solar Cells, Int. J. Electrochem. Sci., 7 (2012) 6910
- 6919.

t
ip
[186] G. Kovács, Z. Pap, C. Coteț, V. Coșoveanu, L. Baia, V. Danciu, Photocatalytic,
Morphological and Structural Properties of the TiO2-SiO2-Ag Porous Structures Based System,

cr
Materials 8(2015) 1059-1073.

us
[187] M.R. Ayers, AJ. Hunt, Titanium oxide aerogels prepared from titanium metal and
hydrogen peroxide, Mater. Lett. , 34 (1998) 290-293.
an
[188] L. Baia, A. Vulpoi, T. Radu, É. Karácsonyi, A. Dombi, K. Hernádi, V. Danciu, S. Simon,
K. Norén, S.E. Canton, G. Kovács, Zs. Pap, TiO2/WO3/Au nanoarchitectures’ photocatalytic
M
activity “from degradation intermediates to catalysts’ structural peculiarities” Part II: Aerogel
based composites-fine details by spectroscopic means, Appl. Catal. B: Environmental, 148-149
(2014) 589-600.
e d

[189] L. Brown, A. Anderson, M. Carroll, Fabrication of titania and titania-silica aerogels using
rapid supercritical extraction, J. Sol-Gel Sci. Technol. , 62 (2012) 404-413.
pt

[190] R. Hutter, T. Mallat, A. Baiker, Selective epoxidation of α-isophorone with mesoporous

ce

titania–silica aerogels and tert-butyl hydroperoxide, J. Chem. Soc., Chem. Commun., (1995)
2487-2488.
Ac

[191] L. Chen, J. Zhu, Y.-M. Liu, Y. Cao, H.-X. Li, H.-Y. He, W.-L. Dai, K.-N. Fan,
Photocatalytic activity of epoxide sol–gel derived titania transformed into nanocrystalline
aerogel powders by supercritical drying, J. Mol. Catal. A: Chemical 255 (2006) 260-268.

[192] S. Y. Chai, Y. J. Kim, W. I. Lee, Photocatalytic WO3/TiO2 nanoparticles working under

visible light, J. Electroceram, 17 (2006) 909-912.

87
 

Page 87 of 96
[193] H. Li, S. G. Sunol, A. K. Sunol, Development of titanium-dioxide-based aerogel catalyst
with tunable nanoporosity and photocatalytic activity, Nanotechnology 23 (2012) 294012-
294017.

[194] S. Cao, K. L. Yeung, P.-L. Yue, Preparation of freestanding and crack-free titania–silica
aerogels and their performance for gas phase, photocatalytic oxidation of VOCs, Appl. Catal. B:

t
ip
Environmental, 68 (2006) 99-108.

[195] WI. Kim, IK. Hong, Synthesis of monolithic titania-silica composite aerogels with

cr
supercritical drying process, J. Ind. Eng. Chem., 9 (2003) 728-734.

us
[196] B. Malinowska, J. Walendziewski, D. Robert, J.V. Weber, M. Stolarski, The study of
photocatalytic activities of titania and titania–silica aerogels, Appl. Catal. B: Environ., 46 (2003)
441-451. an
[197] M. Schneider, A. Baiker, High-surface-area titania aerogels: preparation and structural
M
properties, J. Mater. Chem., 2 (1992) 587-589.

[198] AJ. Maira, KL. Yeung, CY. Lee, PL. Yue, CK. Chan, Size effects in gas-phase photo-
d

oxidation of trichloroethylene using nanometer-sized TiO2 catalysts, J. Catal., 192 (2000) 185-
e

196.
pt

[199] S. Yoda, K. Ohtake, Y. Takebayashi, T. Sugeta, T. Sako, T. Sato, Preparation of SiO2-

TiO2 Aerogels Using Supercritical Impregnation, J. Sol-Gel Sci. Technol. , 19 (2000) 719-723.
ce

[200] S. Yoda, K. Ohtake, Y. Takebayashi, T. Sugeta, T. Sako, T. Sato, Preparation of titania-

impregnated silica aerogels and their application to removal of benzene in air, J. Mater. Chem.,
Ac

10 (2000) 2151-2156.

[201] N. Yao, S. Cao, K. L. Yeung, Mesoporous TiO2–SiO2 aerogels with hierarchal pore
structures, Micropor. Mesopor. Mater. , 117 (2009) 570-579.

[202] Y. Boyjoo, H. Sun, J. Liu, V. K. Pareek, S. Wang, A review on photocatalysis for air
treatment: From catalyst development to reactor design, Chem. Eng. J., 310 (2017) 537-559.

88
 

Page 88 of 96
[203] J. Lasek, Y.-H. Yu, J.C.S. Wu, Removal of NOx by photocatalytic processes, J.
Photochem. Photobio. C: Photochem. Rev., 14 (2013) 29-52.

[204] S. Yamazoe, Y. Masutani, K. Teramura, Y. Hitomi, T. Shishido, T. Tanaka, Promotion

effect of tungsten oxide on photo-assisted selective catalytic reduction of NO with NH3 over
TiO2, Appl. Catal. B: Environ., 83 (2008) 123-130.

t
ip
[205] S. Yamazoe, Y. Masutani, T. Shishido, T. Tanaka, Metal oxide promoted TiO2 catalysts
for photo-assisted selective catalytic reduction of NO with NH3, Res. Chem. Intermediate 34

cr
(2008) 487-494.

us
[206] M. Polat, A. M. Soylu, D. A. Erdogan, H. Erguven, E. I. Vovk, E. Ozensoy, Influence of
the sol–gel preparation method on the photocatalytic NO oxidation performance of TiO2/Al2O3
binary oxides, Catal. Today 241 (2015) 25-32. an
[207] A. M. Soylu, M. Polat, D. A. Erdogan, Z. Say, C. Yıldırım, Ö. Birer, E. Ozensoy, TiO2–
M
Al2O3 binary mixed oxide surfaces for photocatalytic NOx abatement, Appl. Surf. Sci., 318
(2014) 142-149.
d

[208] S. J. Kim, P. Raut, S. C. Jana, G. Chase, Electrostatically Active Polymer Hybrid Aerogels
e

for Airborne Nanoparticle Filtration, ACS Appl. Mater. Interfaces 9(2017) 6401−6410.
pt

[209] M. Kampa, E. Castanas, Human Health Effects Of Air Pollution, Environ. Pollut. , 151
(2008) 362−367.
ce

[210] S. J. Kim, G. Chase, S. C. Jana, The Role Of Mesopores In Achieving High Efficiency
Airborne Nanoparticle Filtration Using Aerogel Monoliths, Sep. Purif. Technol., 166 (2016)
Ac

48−54.

[211] S. J. Kim, G. Chase, S. C. Jana, Polymer Aerogels For Efficient Removal Of Airborne
Nanoparticles, Sep. Purif. Technol. , 156 (2015) 803−808.

[212] M. S. Ahmed, Y. A. Attia, Multi-Metal Oxide Aerogel For Capture Of Pollution Gases
From Air, Appl. Therm. Eng. , 18 (1998) 787−797.

89
 

Page 89 of 96
[213] M.T. Guise, B. Hosticka, B.C. Earp, P.M. Norris, An experimental investigation of aerosol
collection utilizing packed beds of silica aerogel microsphere, J. Non-Cryst. Solids, 285 (2001)
317-322.

[214] A. Vohra, D.Y. Goswami, D.A. Deshpande, S.S. Block, Enhanced photocatalytic
disinfection of indoor air, Appl. Catal. B Environ., 64 (2006) 57-65.

t
ip
[215] Y. Kikuchi, K. Sunada, T. Iyoda, K. Hashimoto, A. Fujishima, Inactivation of
Microorganisms on the Photocatalytic Surfaces in Air, J. Photoch. Photobio. A 106 (1997) 51-

cr
56.

us
[216] K. Sunada, T. Watanabe, K. Hashimoto, Antibacterial Activity of TiO2/Ti Composite
Photocatalyst Films Treated by Ultrasonic Cleaning, J. Photoch. Photobio. A, 156 (2003) 227-
233. an
[217] S. Cao, Preparation, characterization and applications of monolithic titania-silica aerogels,
M
School of Engineering, Hong Kong University of Science and Technology, 2007.

[218] B. Krishnakumar, M. Swaminathan, Influence of operational parameters on photocatalytic

d

degradation of a genotoxic azo dye Acid Violet 7 in aqueous ZnO suspensions, Spectrochim.
e

Acta A. Mol. Biomol. Spectrosc. , 81 (2011) 739-744.

pt

[219] M. Antonopoulou, E. Evgenidou, D. Lambropoulou, I. Konstantinou, A review on

advanced oxidation processes for the removal of taste and odor compounds from aqueous media,
ce

Water Res., 5 3 (2014) 215-234.

[220] A. Asghar, A. A. Abdul Raman, W.M.A.W. Daud, Advanced oxidation processes for in-
Ac

situ production of hydrogen peroxide/hydroxyl radical for textile wastewater treatment: a review,
J Clean Prod., 87 (2015) 826-838.

[221] M.N. Chong, A.K. Sharma, S. Burn, C.P. Saint, Feasibility study on the application of
advanced oxidation technologies for decentralised wastewater treatment, J. Clean. Prod. , 35
(2012) 230-238.

90
 

Page 90 of 96
[222] J. Fernandez, J. Bandara, A. Lopez, P. Buffat, J. Kiwi, Photoassisted Fenton degradation of
nonbiodegradable azo dye (Orange II) in Fe-free solutions mediated by cation transfer
membranes, Langmuir 15 (1999) 185-192.

[223] J.J. Pignatello, E. Oliveros, A. MacKay, Advanced oxidation processes for organic
contaminant destruction based on the Fenton reaction and related chemistry, Crit. Rev. Environ.

t
ip
Sci. Technol. , 36 (2006) 1-84.

[224] A.L.-T. Pham, C. Lee, F.M. Doyle, D.L. Sedlak, A silica-supported iron oxide catalyst

cr
capable of activating hydrogen peroxide at neutral pH values, Environ. Sci. Technol. , 43 (2009)

us
8930-8935.

[225] E.G. Garrido-Ramirez, B.K.G. Theng, M.L. Mora, Clays and oxide minerals as catalysts
an
and nanocatalysts in Fenton-like reactions - a review, Appl. Clay Sci., 47 (2010) 182-192.

[226] H. Lim, J. Lee, S. Jin, J. Kim, J. Yoon, T. Hyeon, Highly active heterogeneous Fenton
M
catalyst using iron oxide nanoparticles immobilized in alumina coated mesoporous silica, Chem.
Commun., 4 (2006) 463-465.
d

[227] A. Santos, P. Yustos, S. Rodríguez, F. Garcia-Ochoa, M. de Gracia, Decolorization of

e

Textile Dyes by Wet Oxidation Using Activated Carbon as Catalyst, Ind. Eng. Chem. Res., 46
(2007) 2423-2427.
pt

[228] J. Herney-Ramirez, M. A. Vicente, L.M. Madeirac, Heterogeneous photo-Fenton oxidation

ce

with pillared clay-based catalysts for wastewater treatment: A review, Appl. Catal. B: Environ.,
98 (2010) 10-26.
Ac

[229] R. Gonzalez-Olmos, M. J. Martin, A. Georgi, F.-D. Kopinke, I. Oller, S. Malat, Fe-zeolites

as heterogeneous catalysts in solar Fenton-like reactions at neutral pH, Appl Catal B:
Enviromental, 125 (2012) 51-58.

[230] Y. Li, F. Hung, L. J. Hope-Weeks, W. Yan, Fe/Al binary oxide aerogels and xerogels for
catalytic oxidation of aqueous contaminants, Sep. Purif. Technol., 156 (2015) 1035-1040.

91
 

Page 91 of 96
[231] J.H. Ramirez, F.J. Maldonado-Hodar, A.F. Pe´rez-Cadenas, C. Moreno-Castilla, C.A.
Costa, L.M. Madeira, Azo-dye Orange II degradation by heterogeneous Fenton-like reaction
using carbon-Fe catalysts, Appl. Catal. B: Environmental, 75 (2007) 312-323.

[232] Y. Hardjono, H. Sun, H. Tian, C.E. Buckley, S. Wang, Synthesis of Co oxide doped
carbon aerogel catalyst and catalytic performance in heterogeneous oxidation of phenol in water,

t
ip
Chem. Eng. J., 174 (2011) 376- 382.

[233] N.K. Daud, M.A. Ahmad, B.H. Hameed, Decolorization of Acid Red 1 dye solution by

cr
Fenton-like process using Fe–Montmorillonite K10 catalys, Chem. Eng. J., 165 (2010) 111-116.

us
[234] M. T. Amin, A. A. Alazba, U. Manzoor, A Review of Removal of Pollutants from
Water/Wastewater Using Different Types of Nanomaterials, Adv. Mater. Sci. Eng. , 2014 (2014)
1-24. an
[235] M. Sanchez-Polo, J. Rivera-Utrilla, U. von Gunten, Metal-doped carbon aerogels as
M
catalysts during ozonation processes in aqueous solutions, Water Res., 40 (2006) 3375 - 3384.

[236] E. Hu, X. Wu, S. Shang, X.-m. Tao, S.-x. Jiang, L. Gan, Catalytic ozonation of simulated
d

textile dyeing wastewater using mesoporous carbon aerogel supported copper oxide catalyst, J
e

Clean Prod., 112 (2016) 4710-4718.

pt

[237] X. Huang, C. Tan, Z. Yin, H. Zhang, 25th anniversary article: Hybrid nanostructures based
on two-dimensional nanomaterials, Adv. Mater. , 26 (2014) 2185−2204.
ce

[238] S. Cao, K.L. Yeung, P.-L. Yue, An investigation of trichloroethylene photocatalytic

oxidation on mesoporous titania-silica aerogel catalysts, Appl. Catal. B: Environmental, 76
Ac

(2007) 64-72.

[239] S. Cao, K.L. Yeung, J.K.C. Kwan, P.M.T. To, S.C.T. Yu, An investigation of the
performance of catalytic aerogel filters, Appl. Catal. B: Environmental, 86 (2009) 127-136.

[240] W. Liu, J. Cai, Z. Li, Self-Assembly of Semiconductor Nanoparticles/Reduced Graphene

Oxide (RGO) Composite Aerogels for Enhanced Photocatalytic Performance and Facile
Recycling in Aqueous Photocatalysis, ACS Sustainable Chem. Eng., 3 (2015) 277-282.

92
 

Page 92 of 96
[241] X. Shao, W. Lu, R. Zhang, F. Pan, Enhanced photocatalytic activity of TiO2-C hybrid
aerogels for methylene blue degradation, Sci. Rep., 3 (2013) 3018.

[242] F. Orellana-García, M. A. Álvarez, M. Victoria López-Ramón, J. Rivera-Utrilla, M.

Sánchez-Polo, M. Á. Fontecha-Cámara, Photoactivity of organic xerogels and aerogels in the
photodegradation of herbicides from waters, Appl. Catal. B: Environmental, 181 (2016) 94-102.

t
ip
[243] J. Cai, W. Liu, Z. Li, One-pot self-assembly of Cu2O/RGO composite aerogel for
aqueousphotocatalysis, Appl. Surf. Sci., 358 (2015) 146-151.

cr
[244] X. Li, S. Yang, J. Sun, P. He, X. Xu, G. Ding, Tungsten oxide nanowire-reduced graphene

us
oxide aerogel for high-efficiency visible light photocatalysis, Carbon, 78 (2014) 38-48.

[245] Y. Jin, M. Wu, G. Zhao, M. Li, Photocatalysis-enhanced electrosorption process for

an
degradation of high-concentration dye wastewater on TiO2/carbon aerogel, Chem. Eng. J., 168
(2011) 1248-1255.
M
[246] D. Bamba, M. Coulibaly, C. I. Fort, C. L. CoteSt, Z. Pap, K. Vajda, E. G. Zoro, N. Alfred
Yao, V. Danciu, D. Robert, Synthesis and characterization of TiO2/C nanomaterials:
d

Applications in water treatment, Phys. Status Solidi B 252 (2015) 2503-2511

e

[247] M. Miao, G. Wang, S. Cao, X. Feng, J. Fang, L. Shi, TEMPO-mediated oxidized winter
pt

melon-based carbonaceous aerogel as an ultralight 3D support for enhanced photodegradation of

organic pollutants, Phys. Chem. Chem. Phys., 17 (2015) 24901-24907.
ce

[248] Z. Zhou, X. Zhang, C. Lu, L. Lan, G. Yuan, Polyaniline-decorated cellulose aerogel

nanocomposite with strong interfacial adhesion and enhanced photocatalytic activity, RSC Adv.,
Ac

4 (2014) 8966-8972.

[249] S.K. Papageorgiou, F.K. Katsaros, E.P. Favvas, G. Em. Romanos, C.P. Athanasekou, K.G.
Beltsios, O.I. Tzialla, P. Falaras, Alginate fibers as photocatalyst immobilizing agents applied in
hybrid photocatalytic/ultrafiltration water treatment processes, Water Res., 46 (2012) 1858-1872.

93
 

Page 93 of 96
[250] M. Shi, W. Wei, Z. Jiang, H. Han, J. Gao, J. Xie, Biomass-derived Multifunctional
TiO2/Carbonaceous Aerogel Composite for the Highly Efficient Photocatalyst, RSC Adv., 6
(2016) 25255-25266.

[251] H. S. Kibombo, A. S. Weber, C.-M. Wu, K. R. Raghupathi, R. T. Koodalia, Effectively

dispersed europium oxide dopants in TiO2 aerogel supports for enhanced photocatalytic

t
ip
pollutant degradation, J. Photochem. Photobiol. A: Chemistry 269 (2013) 49- 58.

[252] Z. PAP, A. RADU, I. J. HIDI, G. MELINTE, L. DIAMANDESCU, T. POPESCU, L.

cr
BAIA, V. DANCIU, M. BAIA, Behavior of gold nanoparticles in a titania aerogel matrix:

us
Photocatalytic activity assessment and structure investigations, Chinese J. Catal. , 34 (2013)
734-740.

an
[253] J. Puskelova, L. Baia, A. Vulpoi, M. Baia, M. Antoniadou, V. Dracopoulos, E. Stathatos,
K. Gabor, Z. Pap, V. Danciuf, P. Lianos, Photocatalytic hydrogen production using TiO2–Pt
aerogels, Chem. Eng. J., 242 (2014) 96-101.
M
[254] Y. Yu, M. Zhu, W. Liang, S. Rhodes, J. Fang, Synthesis of Silica-Titania Composite
Aerogel Beads for the Removal of Rhodamine B in Water, RSC Adv., 5 (2015) 72437-72443.
e d

[255] M. S. Ahmed, Y. A. Attia, Aerogel materials for photocatalytic detoxification of cyanide

wastes in water J. Non-Cryst. Solids 186 (1995) 402-407.
pt

[256] Z. Deng, J. Wang, Y. Zhang, Z. Weng, Z. Zhang, B: Zhou, J. Shen, L. Cheng, Preparation
ce

and photocatalytic activity of TiO2-SiO2 binary aerogels, Nanostruct. Mater., 11 (1999) 1313-
1318.
Ac

[257] X. Gao, I. E. Wachs, Titania-silica as catalysts: molecular structural characteristics and

physico-chemical properties, Catal. Today 51 (1999) 233-254.

[258] J. Zhu, J. Xiea, X. Lüa, D. Jianga, Synthesis and characterization of superhydrophobic

silica and silica/titania aerogels by sol–gel method at ambient pressure, Colloids and Surfaces A:
Physicochem. Eng. Aspects 342 (2009) 97-101.

94
 

Page 94 of 96
[259] G. Zu, J. Shen, W. Wang, L. Zou, Y. Lian, Z. Zhang, Silica-titania composite aerogel
photocatalysts by chemical liquid deposition of titania onto nanoporous silica scaffolds, ACS
Appl. Mater. Interfaces, 7 (2015 ) 5400-5409.

[260] A. A. Ismail, I. A. Ibrahim, Impact of supercritical drying and heat treatment on physical
properties of titania/silica aerogel monolithic and its applications, Appl. Catal., A: General, 346

t
ip
(2008) 200-205.

[261] P. Serp, J. L. Figueiredo, J. L. Faria, W. Wang, Carbon Materials in Photocatalysis, in: P.

cr
Serp, J. L. Figueiredo (Eds.) Carbon Materials for Catalysis, John Wiley & Sons, Inc.2008.

us
[262] S. Sakthivel, H. Kisch, Daylight photocatalysis by carbon-modified titanium dioxide,
Angew. Chem. Int. Ed. , 42 (2003) 4908-4911
an
[263] M. Toyoda, T. Yano, B. Tryba, S. Mozia, T. Tsumura, M. Inagaki, Preparation of carbon-
coated Magneli phases TinO2n21 and their photocatalytic activity under visible light, Appl.
M
Catal. B: Environmental, 88 (2009) 160-164

[264] K. Woan, G. Pyrgiotakis, W. S. Sigmund, Photocatalytic carbon canotube-TiO2

d

composite, Adv. Mater. , 21 (2009) 2233-2239

e

[265] M. Liu, L. Gan, Y. Pang, Z. Xu, Z. Hao, L. Chen, Synthesis of titania–silica aerogel-like
pt

microspheres by a water-in-oil emulsion method via ambient pressure drying and their
photocatalytic properties, Colloids and Surfaces A: Physicochem. Eng. Aspects 317 (2008) 490-
ce

495.

[266] Y. N. Kim, G. N. Shao, S. J. Jeon, S. M. Imran, P. B. Sarawade, H.T. Kim, Sol–gel

Ac

synthesis of sodium silicate and titanium oxychloride based TiO2–SiO2 aerogels and their
photocatalytic property under UV irradiation, Chem. Eng. J., 231 (2013) 502-511.

[267] L. Luo, A. T. Cooper, M. Fan, Preparation and application of nanoglued binary titania–
silica aerogel, J Hazard Mater, 161 (2009) 175-182.

95
 

Page 95 of 96
[268] C. Fan, Q.L. n, T. Ma, J. Shen, Y. Yang, H. Tang, Y. Wang, J. Yang, Fabrication of 3D
CeVO4/graphene aerogels with efficient visible-light photocatalytic activity, Ceram. Int., 42
(2016) 10487-10492.

[269] T.-Y. Wei, C.-Y. Kuo, Y.-J. Hsu, S.-Y. Lu, Y.-C. Chang, Tin oxide nanocrystals
embedded in silica aerogel: Photoluminescence and photocatalysis, Micropor. Mesopor. Mater. ,

t
ip
112 (2008) 580-588.

[270] V. Vaiano, O. Sacco, D. Sannino, P. Ciambelli, S. Longo, V. Venditto, G. Guerra, N-

cr
doped TiO2/s-PS aerogels for photocatalytic degradation of organic dyes in wastewater under

us
visible light irradiation, J. Chem. Technol. Biotechnol., 89 (2014) 1175-1181.

an
M
e d
pt
ce
Ac

96
 

Page 96 of 96